JPH01213387A - Fluorescent substance slurry for preparing fluorescent film - Google Patents
Fluorescent substance slurry for preparing fluorescent filmInfo
- Publication number
- JPH01213387A JPH01213387A JP12369588A JP12369588A JPH01213387A JP H01213387 A JPH01213387 A JP H01213387A JP 12369588 A JP12369588 A JP 12369588A JP 12369588 A JP12369588 A JP 12369588A JP H01213387 A JPH01213387 A JP H01213387A
- Authority
- JP
- Japan
- Prior art keywords
- phosphor
- slurry
- zns
- zinc
- 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.)
- Granted
Links
- 239000002002 slurry Substances 0.000 title claims abstract description 70
- 239000000126 substance Substances 0.000 title abstract description 5
- 239000011701 zinc Substances 0.000 claims abstract description 101
- 239000007864 aqueous solution Substances 0.000 claims abstract description 26
- 238000004381 surface treatment Methods 0.000 claims abstract description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 18
- -1 zinc halide Chemical class 0.000 claims abstract description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000002270 dispersing agent Substances 0.000 claims abstract description 11
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 10
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims abstract description 8
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims abstract description 8
- 229960001763 zinc sulfate Drugs 0.000 claims abstract description 8
- 229910000368 zinc sulfate Inorganic materials 0.000 claims abstract description 8
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 7
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 7
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 6
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 claims abstract description 6
- 150000003752 zinc compounds Chemical class 0.000 claims abstract description 5
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000000908 ammonium hydroxide Substances 0.000 claims abstract description 3
- 239000004246 zinc acetate Substances 0.000 claims abstract description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 312
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 6
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 6
- 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
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 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
- 230000035945 sensitivity Effects 0.000 abstract description 22
- 239000000203 mixture Substances 0.000 abstract description 14
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 abstract 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 65
- 238000012864 cross contamination Methods 0.000 description 38
- 238000000576 coating method Methods 0.000 description 26
- 239000011248 coating agent Substances 0.000 description 25
- 238000003756 stirring Methods 0.000 description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 19
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 17
- 239000000725 suspension Substances 0.000 description 16
- 239000002245 particle Substances 0.000 description 15
- 238000002156 mixing Methods 0.000 description 14
- 238000001035 drying Methods 0.000 description 13
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 13
- 239000010949 copper Substances 0.000 description 12
- 239000001054 red pigment Substances 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- 238000010908 decantation Methods 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 239000006228 supernatant Substances 0.000 description 8
- 238000011109 contamination Methods 0.000 description 7
- 239000011787 zinc oxide Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 230000007423 decrease Effects 0.000 description 5
- 239000010931 gold Substances 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 239000011575 calcium Substances 0.000 description 3
- 229910052681 coesite Inorganic materials 0.000 description 3
- 229910052906 cristobalite Inorganic materials 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 238000004062 sedimentation Methods 0.000 description 3
- 229910052682 stishovite Inorganic materials 0.000 description 3
- 229910052905 tridymite Inorganic materials 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-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
- 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
- 229910052791 calcium Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910052802 copper 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
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-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
- 239000000843 powder Substances 0.000 description 2
- 238000007581 slurry coating method Methods 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 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
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 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
- 229910052793 cadmium Inorganic materials 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
- 238000009125 cardiac resynchronization therapy Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 230000001678 irradiating effect Effects 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
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- DWDQAMUKGDBIGM-UHFFFAOYSA-N phosphanylidyneyttrium Chemical compound [Y]#P DWDQAMUKGDBIGM-UHFFFAOYSA-N 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
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000004528 spin coating Methods 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
- 238000005406 washing Methods 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Landscapes
- Luminescent Compositions (AREA)
Abstract
Description
【発明の詳細な説明】 本発明は蛍光膜作成用蛍光体スラリーに関する。[Detailed description of the invention] The present invention relates to a phosphor slurry for making a phosphor film.
さらに詳しくは本発明は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
。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.
周知のように、カラーテレビジョ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ブ
をフェ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ョンブラウン管の蛍光膜は光
印刷法によって作成される。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ェースプレー
ト全面に塗布しくスラリー塗布）、シかる後塗布面に所
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（樹脂未硬化部分）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ブを形成する。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、フェー
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。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 created 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 a spin coating method (slurry coating), and after coating, 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). Thereafter, the portion irradiated with energy rays (uncured portion of the resin) is dissolved and removed using a solvent or the like (development) to form dots or stripes made of the first luminescent component phosphor. For the second and third luminescent component phosphors, the same series of slurry coating, 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 energy beam irradiation must be controlled so that the dots or stripes made of the first, second, and third luminescent component phosphors do not overlap each other and are repeatedly and regularly arranged on the face plate. Needless to say, it won't happen. 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.
上述の蛍光体スラリーを用いる光印刷法によってカラー
テレビジョンブラウン管の蛍光膜を作成するにあたって
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フェ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ブを形成すること、（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、調製方法等についで
あるいは蛍光体スラリーに用いるカラーテレビジョン用
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。In creating a phosphor film for color television CRTs by the optical printing method using the above-mentioned phosphor slurry, it is necessary to (1) form dense dots or stripes with sufficient thickness; (3) one luminescent component phosphor does not mix with other luminescent component phosphors, that is, color mixture does not occur; (4) fluorescence The composition and preparation method of phosphor slurry have traditionally been developed in order to satisfy the above requirements, and color televisions used for phosphor slurry have been developed. Various studies have been conducted on the surface treatment of phosphors (blue, green, and red emitting component phosphors) for use in light emitting devices, and current phosphor slurries satisfy each of the above requirements to some extent.
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。However, since higher quality fluorescent films are always required commercially, it is desired to further improve each of the above points.
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。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.
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。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.
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。Another object of the present invention is to provide a phosphor slurry for forming a phosphor film with high exposure sensitivity.
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、２７０４７２８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。Incidentally, in order to improve the dispersibility regarding the above-mentioned item (1), it has been known that 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. (Tokuko Sho 50-15747)
(see USP No. 2704728). However, this surface treatment method differs in structure and effect from the treatment used in the present invention.
上記本発明の目的は特定の蛍光体スラリーによって達成
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。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.
また、従来カラーテレビジョ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ョン用蛍光体の
蛍光体スラリー中における分散性を改良しくこれらカラ
ーテレビジョ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
よっ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。In addition, conventional color television phosphors include silicon dioxide and
We have developed a substance that improves the dispersibility of color television phosphors in phosphor slurry by attaching phosphates such as magnesium, zinc, calcium, aluminum, etc. It is known that a good fluorescent film can be obtained by using a dispersing agent (hereinafter referred to as a "dispersing agent" in the specification). Can be used together.
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
ビジョ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、従って硬化のための紫
外線照射時間（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。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 ultraviolet irradiation time (exposure time) for curing can be shortened, and work efficiency can be increased.
以下本発明の詳細な説明する。The present invention will be explained in detail below.
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。The phosphor slurry of the present invention includes, for example, the steps described below.
まず純水中に蛍光体を入れ、充分に懸濁させる。First, put the phosphor in pure water and suspend it thoroughly.
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）ｚと
略称する］を析出せしめる。Next, an appropriate amount of an aqueous solution containing zinc ions is added to this suspension, and then an alkali is added to the suspension containing zinc ions to adjust the pH value of the suspension to 7.5 to 11. A surface treatment substance typified by zinc [hereinafter abbreviated as Zn(OH)z] is deposited.
析出した微粒子のＺｎ（ＯＨ）ｚは蛍光体表面に吸着さ
れる。懸濁液を放置し、Ｚｎ （ＯＨ）ｚ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ョン
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。The precipitated fine particles of Zn(OH)z are adsorbed on the surface of the phosphor. The suspension is allowed to stand to allow the phosphor to which the Zn (OH)z 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.
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（Ｚｎ Ｓ Ｏａ ） 、酢酸亜鉛［Ｚｎ
（ＣＨ３Ｃｏｏ）ｚ ］ 、硝酸亜鉛［Ｚｎ（ＮＯ
３） ｚ ］ 、ハロゲン化亜鉛（Ｚ ｎ Ｘ ２ 、
Ｘは弗素を除くハロゲン）等の水溶液が用いられる。Examples of aqueous solutions containing zinc ions include water-soluble zinc compounds such as zinc sulfate (ZnSOa), zinc acetate [Zn
(CH3Coo)z], zinc nitrate [Zn(NO
3) z], zinc halide (ZnX2,
An aqueous solution of X is a halogen other than fluorine) is used.
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（Ｎａ ＯＨ）、水
酸化カリウム（ＫＯＨ） 、水酸化アンモニウム（ＮＨ
，ＯＨ）等が水溶液として用いられる。ＮＨ，ＯＨ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）ｚが析出しないので、ＰＭ値が１０を越えない
ように注意する必要がある。In addition, alkali hydroxide is used as the alkali for adjusting the pH value, such as sodium hydroxide (NaOH), potassium hydroxide (KOH), ammonium hydroxide (NH
, OH) etc. are used as an aqueous solution. When using NH and OH, care must be taken to ensure that the PM value does not exceed 10, since if excessively added, soluble ammine complex ions will be generated and Zn (OH)z will not precipitate.
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）ｚ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）ｚがほとんどそのまま残留する。Drying is carried out at a temperature below 250°C, preferably below 200°C. When drying is carried out at a temperature higher than 250° C., the Zn (OH)z adhering to the phosphor changes to a zinc oxide compound (hereinafter abbreviated as ZnO), so that the phosphor used in the present invention cannot be obtained. When drying at 200 to 250°C, some of the Zn(OH)2 converts to ZnO (naturally, the higher the temperature, the higher the rate of conversion to ZnO), but the ZnO produced does not have any adverse effect on the characteristics of the phosphor slurry. It's not a thing. When drying is performed at a temperature of 200° C. or lower, almost no conversion to ZnO occurs, and Zn(OH)z remains almost as it is.
本発明に使用されるカラーテレビジョン用蛍光体に付け
られるＺｎ（ＯＨ）ｚの量はカラーテレビジョン用蛍光
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）ｚ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って蛍光膜と
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ョン用蛍光体、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）ｚと選択的に反応し、可溶性の
アンミン錯イオンを生じる。The amount of Zn(OH)z added to the color television phosphor used in the present invention is more than 0 parts by weight and 0.7 parts by weight or less based on 100 parts by weight of the color television phosphor. If the amount of Zn (OH)z deposited is more than 0.7 parts by weight, the dispersibility of the obtained phosphor in the phosphor slurry gradually deteriorates, resulting in color mixture when formed into a phosphor film. This is not preferable because it becomes noticeable. A more preferable amount of Zn(OH)2 deposited is 0.01 to 0.5 parts by weight. Note that Zn attached to the phosphor
It is convenient to use concentrated ammonia water to quantify (OH)2. Concentrated ammonia water does not react with color television phosphors, which are mainly sulfides or oxides, or with ZnO produced when high drying temperatures are used, but it selectively reacts with Zn(OH)z. Generates soluble ammine complex ions.
従っ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ってＺｎ
（ＯＨ）ｚ付着量を知ることができる。Therefore, by treating the phosphor of the present invention with concentrated ammonia water, Zn
By dissolving and separating (OH)2 as an ammine complex ion and quantifying this ammine complex ion, Zn
You can know the amount of (OH)z attached.
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ョン用蛍光体に従
来の方法で分散剤を付着せしめ、その後上述の方法でＺ
ｎ （ＯＨ）ｚを付着せしめてもよいし、あるいはそ
の逆であってもよい。分散剤としては二酸化珪素（Ｓｉ
０２ ） 、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［Ｍｇ
３ （Ｐｏｔ ）ｚ、Ｚｎ３ （Ｐｏｔ）ｚ、Ｃ
ａ３ （ＰＯａ）ｚ、Ａ免Ｐｏｔ 、Ｍｇ （ＰＯ３
）２ 、Ｚｎ （ＰＯ３）２、Ｃａ （ＰＯ３）ｚ
、Ａｉ（ＰＯ３）３、Ｍｇ２ Ｐ２０７ 、Ｚｎ２ Ｐ
２０Ｔ 、Ｃａ２ ｐ２ｏ、等］が用いられるが、特に
５１０２を用いるのが好ましい。分散剤は従来知られて
いる方法によって蛍光体に付けられる。例えば５ＩＯ２
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５ＩＯ２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。Note that when a dispersant is used in conjunction with the phosphor used in the present invention, the dispersant is first applied to the phosphor for color television using a conventional method, and then Z is coated using the method described above.
n (OH)z may be deposited, or vice versa. Silicon dioxide (Si
02), ortho, meta or pyrophosphates of magnesium, zinc, calcium, aluminum etc. [Mg
3 (Pot)z, Zn3 (Pot)z, C
a3 (POa)z, Amen Pot, Mg (PO3
)2, Zn (PO3)2, Ca (PO3)z
, Ai(PO3)3, Mg2 P207 , Zn2 P
20T, Ca2p2o, etc.], but it is particularly preferable to use 5102. The dispersant is applied to the phosphor by conventionally known methods. For example 5IO2
In this case, 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 5IO2 fine particles, which are simultaneously applied to the surface of the phosphor. A method such as adsorption is adopted.
本発明に用いられる蛍光体、例えばカラーテレビジョン
用蛍光体はカラーテレビジョ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。The phosphors used in the present invention, such as phosphors for color televisions, include all phosphors that can be used as blue, green or red emitting component phosphors of color television cathode ray tube fluorescent films.
このカラーテレビジョン用蛍光体は単一の蛍光体であっ
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（Ｚｎ Ｓ ： Ｃｕ
５Ａ９Ｊ）と金およびアルミニウム付活硫化亜鉛蛍光
体（Ｚｎ Ｓ ： Ａｕ ５Ａ９Ｊ）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ってもよい。ま
た、最近高コントラストカラーテレビジョンブラウン管
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
るカラーテレビジョン用蛍光体はこの顔料付蛍光体であ
ってもよい。従って本明細書における「カラーテレビジ
ョン用蛍光体」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。This color television phosphor may be a single phosphor, or it may be a copper- and aluminum-activated zinc sulfide phosphor (ZnS:Cu), which has recently been put into practical use.
A mixed phosphor such as a green-emitting component phosphor obtained by mixing a gold and aluminum activated zinc sulfide phosphor (ZnS:Au 5A9J) and a gold- and aluminum-activated zinc sulfide phosphor (ZnS:Au 5A9J) 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 an attached phosphor. 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.
特に実用的な点から好ましいカラーテレビジョン用蛍光
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（Ｚｎ Ｓ ：Ａｇ、Ａ９Ｊ）、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：Ａｇ５ＡＱ、蛍光体等
、緑色発光成分蛍光体として上述のＺｎＳ：Ｃｕ、ＡＱ
、蛍光体とＺｎＳ：Ａｕ、ＡＱ、蛍光体の混合蛍光体、
ＺｎＳ：Ｃｕ、Ａ９Ｊ蛍光体、金、銅およびアルミニウ
ム付活硫化亜鉛蛍光体（Ｚｎ Ｓ ：Ａｕ、Ｃｕ、Ａ９
Ｊ）、銅およびアルミニウム付活硫化亜鉛・カドミウム
蛍光体［（ＺｎＳＣｄ）Ｓ：Ｃｕ５Ａ、Ｑ、］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：Ｅｌｌ）、ユーロピウム付活酸化
イツトリウム蛍光体（Ｙ２０３ ： Ｅｕ）、べんがら
赤色顔料粒子材Ｙ２０２ Ｓ ： Ｅｕ蛍光体、べんが
ら赤色顔料粒子材Ｙ２０３ ： Ｅｕ蛍光体、硫セレ
ン化カドミウム赤色顔料粒子付Ｙ２０２ Ｓ ： Ｅｕ
蛍光体、硫セレン化カドミウム赤色顔料粒子付Ｙ２０３
： Ｅｕ蛍光体等が挙げられる。Particularly preferred phosphors for color television from a practical point of view include silver-activated zinc sulfide phosphors (ZnS:Ag) and silver- and aluminum-activated zinc sulfide phosphors (ZnS:Ag, A9J) as blue-emitting phosphors. ), ZnS:Ag phosphor with cobalt aluminate blue pigment particles, ZnS:Ag5AQ with cobalt aluminate blue pigment particles, phosphor, etc., ZnS:Cu, AQ mentioned above as green emitting component phosphor
, phosphor and ZnS: mixed phosphor of Au, AQ, phosphor,
ZnS: Cu, A9J phosphor, gold, copper and aluminum activated zinc sulfide phosphor (ZnS: Au, Cu, A9
J), copper- and aluminum-activated zinc sulfide/cadmium phosphor [(ZnSCd)S:Cu5A,Q,], europium-activated yttrium oxysulfide phosphor (Y2O2S:Ell), europium-activated oxidation as a red-emitting phosphor, etc. Yttrium phosphor (Y203: Eu), red pigment particle material Y202S: Eu phosphor, red pigment particle material Y203: Eu phosphor, with cadmium selenide sulfate red pigment particles Y202S: Eu
Phosphor, cadmium selenide sulfide with red pigment particles Y203
: Examples include Eu phosphor.
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。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 light emitting component phosphor.
カラーテレビジョ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。There are two types of color mixing between the luminescent component phosphors in a color television cathode ray tube phosphor film.
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
あるいはストライブがフェ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
るいはストライブの位置に蛍光体が残留し、これによっ
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ブが形成され
る時、すでに形成されている他の発光成分蛍光体のドツ
トあるいはストライブ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ョン」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ョ
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ブの特性の両方に
依存して生じるものである。One is that when the first or second emissive component phosphor is slurried, exposed, and developed to form dots or stripes on the faceplate, other subsequently formed emissive component phosphors are This is a case where the phosphor remains at the dots or stripes of the light-emitting component phosphor, resulting in color mixing, and such residual phosphor is called "haze." The other is 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 that has already been formed. The phosphor adheres to and remains on the dots or 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.
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
ンタミネーションのいずれによる混色も著しく改良する
ものである。The phosphor slurry of the present invention significantly improves color mixing due to both haze and cross-contamination as described above.
第１図はＺｎ （ＯＨ）２付着Ｚｎ Ｓ ：Ａｇ蛍光
体（付着量〇も含む）の蛍光体スラリーを用いた時、Ｚ
ｎ（ＯＨ）ｚ付着量とヘイズとの関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
Ｚｎ Ｓ ： Ａｇ蛍光体１００重量部に対して０．１
５重量部のＳＩＯ□が付着しているＺｎＳ：Ａｇ蛍光体
を用いてＺｎ（ＯＨ）ｚ付着量がそれぞれ異なる７種類
のＺｎ （ＯＨ）ｚ付＠ＺｎＳ：Ａｇ蛍光体を製造し
た。この７種類のＺｎ（ＯＨ）ｚ付着Ｚｎ Ｓ ： Ａ
ｇ蛍光体とＺｎ（ＯＨ）ｚが付着してないＺｎ Ｓ ：
Ａｇ蛍光体（０，１５重量％の５ＩＯｚ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ェースプレート上にスト
ライブを形成した。Figure 1 shows the Z
It is a graph showing the relationship between n(OH)z adhesion amount and haze. The graph in FIG. 1 was obtained as follows. First, ZnS: 0.1 per 100 parts by weight of Ag phosphor
Using a ZnS:Ag phosphor to which 5 parts by weight of SIO□ was attached, seven types of Zn(OH)z attached@ZnS:Ag phosphors having different amounts of Zn(OH)z attached were manufactured. These seven types of Zn(OH)z adhesion Zn S: A
g ZnS to which phosphor and Zn(OH)z are not attached:
Eight types of Ag phosphors (0.15% by weight of 5IOz 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.
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。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.
次に得られる各蛍光体スラリーをそれぞれ１６インチブ
ラウン管のフェースプレート上に回転塗布し、乾燥し、
しかる後シャ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ブ状に露光し、温水
により現像してストライブを形成した。なお、上記スト
ライブの作成方法は第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ブを
形成したフェースプレートの一部を拡大投映顕微鏡によ
って１００倍に拡大してスクリーンに写し、未露光部、
すなわちストライブとストライブの間隙部分のスクリー
ン上で２０順×２０１１１１ＩＩ（フェースプレート上
では０．２ｓＸ Ｏ，２ｒＩＪＩＩＩ）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Ｚ
ｎ（ＯＨ）ｚ付着量（Ｚｎ Ｓ ： Ａｇ蛍光体１００
重量部に対する重量部）に対してプロットして第１図の
グラフを得た。Next, each of the obtained phosphor slurries was spin-coated onto the face plate of a 16-inch cathode ray tube, dried,
Thereafter, the coated surface was exposed in stripes by irradiating ultraviolet rays with a high-pressure mercury lamp through a shadow mask, and developed with hot water to form stripes. The method for creating stripes described above was also applied to obtain the graphs shown in FIGS. 2 and 4. A part of the face plate on which stripes were formed as described above was magnified 100 times using a magnifying projection microscope and projected onto a screen, and the unexposed area,
That is, the number of phosphor particles (haze) remaining in 20 order x 201111II (0.2sX O, 2rIJIII on the face plate) was counted on the screen in the gap between the stripes. For each phosphor slurry sample, the number of phosphor particles is counted at two locations, and the average value is calculated as Z for each phosphor sample.
n(OH)z adhesion amount (ZnS: Ag phosphor 100
The graph of FIG. 1 was obtained by plotting against parts by weight (parts by weight).
第１図から明らかなように、Ｚｎ（ＯＨ）ｚ付着量が増
加するに従ってヘイズは減少することが分かる。特にＺ
ｎ（ＯＨ）ｚ付着量が０．５重量部まではＺｎ（ＯＨ）
ｚ付着量増加に対するヘイズの減少は著しく、Ｚｎ（Ｏ
Ｈ）ｚ付着量０．５重量部の場合のヘイズはＺｎ （
ＯＨ）ｚ付着量０の場合の約１／１０となる。As is clear from FIG. 1, it can be seen that the haze decreases as the amount of Zn(OH)z attached increases. Especially Z
Zn(OH) if the amount of n(OH)z deposited is up to 0.5 parts by weight.
The decrease in haze with the increase in the amount of z deposited was remarkable.
H) The haze when the Z coating amount is 0.5 parts by weight is Zn (
OH)z It is about 1/10 of the case where the adhesion amount is 0.
第２図はＺｎ（ＯＨ）ｚ付着Ｚｎ Ｓ ： 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）ｚ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ョンの関係を示すグラフである
。クロスコンタミネーションは次の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ョンであり（「前塗布発光
成分蛍光体とのクロスコンタミネーション」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ョンである（「後塗
布発光成分蛍光体とのクロスコンタミネーション」と呼
ぶことにする）。第２図（Ａ）はＺｎ （ＯＨ）ｚ付
着Ｚｎ Ｓ ： Ａｇ蛍光体（付着量Ｏも含む）のＺｎ
（ＯＨ）２付着量と、その蛍光体の面塗布ＺｎＳ：Ｃｕ
、ＡＱ、緑色発光成分蛍光体とのクロスコンタミネーシ
ョンの関係を示すグラフであり、第２図−（Ｂ）はＺｎ
（ＯＨ）ｚ付着ＺｎＳ：Ａｇ蛍光体（付着量０も含む）
のＺｎ（ＯＨ）ｚ付着量と、その蛍光体の後塗布Ｙ２Ｏ
２Ｓ ： Ｅｕ赤色発光成分蛍光体とのクロスコンタミ
ネーショ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ョン（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。Figure 2 shows Zn when using a phosphor slurry of Zn(OH)z-adhered ZnS:Ag phosphor (including 0 adhesion amount).
It is a graph showing the relationship between the amount of (OH)z adhesion and the cross-contamination of the phosphor with other luminescent component phosphors. There are two possible cases of cross-contamination: One is cross-contamination that adheres to the luminescent component phosphor that has already been applied (hereinafter referred to as "cross-contamination with the pre-applied luminescent component phosphor"), and the other is the one that is applied afterward. This is cross-contamination in which the luminescent component phosphor adheres (hereinafter referred to as "cross-contamination with the post-coated luminescent component phosphor"). Figure 2 (A) shows the Zn of Zn(OH)z adhesion ZnS:Ag phosphor (including the adhesion amount O).
(OH)2 adhesion amount and surface coating of the phosphor ZnS:Cu
, AQ, is a graph showing the cross-contamination relationship with the green light-emitting component phosphor;
(OH)z attached ZnS:Ag phosphor (including 0 attached amount)
Zn(OH)z adhesion amount and its phosphor post-coating Y2O
2S: This is a graph showing the relationship of cross-contamination with the Eu red light-emitting component phosphor. Figure 2-(A)
In and (B), cross-contamination (vertical axis) is represented by the values of blue output/green output and red output/blue output, respectively, and these values were measured as follows.
第２図−（Ａ）については、まずＺｎ Ｓ ： Ｃｕ
。For Figure 2-(A), first ZnS: Cu
.
ＡＱ、緑色発光成分蛍光体［Ｚｎ （ＯＨ）２末処理
］のストライブがあらかじめ形成されているフェースプ
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った。上記作業を行
なった後（当然Ｚｎ Ｓ ： Ａｇ蛍光体のストライブ
は形成されていない）、ＺｎＳ：Ｃｕ、Ａ免蛍光体のス
トライブを３６５０人の紫外線で励起し、発光をハーフ
ミラ−で分割し、分割された２つの光をそれぞれ緑およ
び青のラツテンフィルターを通してフォトマルで受光し
、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）ｚ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）ｚ付着量（Ｚ
ｎ Ｓ ： Ａｇ蛍光体１００重量部に対する重量部）
に対してプロットした。AQ, a phosphor slurry sample was applied onto a face plate on which stripes of green emitting component phosphor [Zn(OH)2 powder treatment] had been formed and dried.
Development was carried out with warm water without exposure. After performing the above operations (obviously, stripes of ZnS:Ag phosphor have not been formed), stripes of ZnS:Cu,A phosphor are excited with 3650 UV rays, and the emitted light is divided by a half mirror. Then, the two divided lights were received by a photomultiplier through green and blue Wratten filters, and the respective outputs were measured to determine the value of blue output/green output. The values of blue output/green output were determined for each phosphor sample, and those with a Zn(OH)z adhesion amount of 0 were normalized as 1, and the Zn(OH)z adhesion amount (Z
nS: parts by weight based on 100 parts by weight of Ag phosphor)
plotted against.
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、現像してストライブを形成した。次に
この試料のストライブが形成されているフェースプレー
ト上にＹ２０□Ｓ ： Ｅｕ 赤色発光成分蛍光体［Ｚ
ｎ （ＯＨ）２末処理コ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った。上記作業を
行なった後（当然Ｙ２０２Ｓ ： Ｅｕ蛍光体のストラ
イブは形成されていない）、試料のストライブを３６５
ＯＡ紫外線で励起し、発光をハーフミラ−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ッテンフィ
ルターを通してフォトマルで受光し、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。Regarding FIG. 2-(B), first, a phosphor slurry sample was applied, exposed, and developed to form stripes. Next, Y20□S:Eu red emitting component phosphor [Z
After applying a slurry of n(OH)2 powder treatment and drying, development was performed with warm water without exposure. After performing the above operations (naturally Y202S: stripes of Eu phosphor are not formed), strip the sample with 365 stripes.
Excite with OA ultraviolet rays, split the emitted light with a half mirror, receive the two split lights through a blue and red Wratten filter, and measure each output to determine the value of red output/green output. I asked for
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）ｚ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 （ＯＲ）２付着量
（Ｚｎ Ｓ ：Ａｇ蛍光体１００重量部に対する重量部
）に対してプロットした。Determine the red output/green output values for each phosphor sample,
A Zn (OH)z adhesion amount of 0 was normalized as 1, and plotted against the Zn (OR)2 adhesion amount (Zn S : parts by weight relative to 100 parts by weight of Ag phosphor) of each phosphor slurry sample.
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Ｚｎ
Ｓ ：Ａｇ蛍光体の前壁布ＺｎＳ：Ｃｕ、Ａ４蛍光体へ
のクロスコンタミネーションおよびＺｎ Ｓ ： Ａｇ
蛍光体への後塗布Ｙ２Ｏ２Ｓ ： Ｅｕ蛍光体のクロス
コンタミネーションが多いことを意味する。In Figure 2-(A) and (B), the larger the values of blue output/green output and red output/blue output, the higher the Zn
Front wall cloth of S:Ag phosphor ZnS:Cu, cross contamination to A4 phosphor and ZnS:Ag
Post-coating Y2O2S on phosphor: This means that there is a lot of cross contamination of Eu phosphor.
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って前塗布発光成分蛍光体への
クロスコンタミネーションは減少することが分かる。特
にＺｎ（ＯＨ）ｚ付着量が０，５重量部まではＺｎ（Ｏ
Ｈ）ｚ付着量増加に対するクロスコンタミネーションの
減少は著しい。As is clear from Figure 2-(A), Zn(OH)
It can be seen that cross-contamination to the pre-applied luminescent component phosphor decreases as the amount of phosphor 2 deposited increases. In particular, when the amount of Zn(OH)z deposited is up to 0.5 parts by weight,
H) The decrease in cross-contamination is remarkable as the amount of z deposition increases.
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ョンはＺｎ （Ｏ
Ｈ）ｚ付着量が０．２乃至０．３重量部まではＺｎ
（ＯＨ）ｚ付着量の増加に伴って減少するが、Ｚｎ
（ＯＨ）ｚ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）ｚ付着量０の場合と同じになる。本発明
においてＺｎ（０）（）ｚ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。Furthermore, as is clear from Figure 2-(B), cross-contamination with the post-applied luminescent component phosphor is caused by Zn (O
H) If the Z adhesion amount is 0.2 to 0.3 parts by weight, Zn
(OH)z decreases with increasing amount of deposited, but Zn
When the (OH)z adhesion amount further increases, it begins to increase,
When the amount of Zn(OH)2 attached is about 0.7 parts by weight, it is the same as when the amount of Zn(OH)z attached is 0. It is based on this knowledge that the upper limit of the amount of Zn(0)()z deposited is set to 0.7 parts by weight in the present invention.
上述のようにＺｎ（ＯＨ）ｚ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ョンが増加す
るようになるのは、その１つの理由としてＺｎ （Ｏ
Ｈ）ｚ付着量がある値以上に大きくなると蛍光体の分散
性が悪くなっ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ブを形成した場合ストラ
イブの背面（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
ンタミネーションが生じやすくなる。Ｚｎ （ＯＨ）
ｚ付着Ｚｎ Ｓ ： 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。As mentioned above, when the amount of Zn(OH)z attached increases, cross contamination with the post-applied luminescent component phosphor increases.One of the reasons for this is that Zn(OH)z
H) This is considered to be because the dispersibility of the phosphor deteriorates when the amount of z attached exceeds a certain value. In other words, when the dispersibility deteriorates, when stripes are formed, unevenness tends to occur on the back surface of the stripes (the surface on which post-coating is performed), which makes cross-contamination with the post-coated light-emitting component phosphor more likely to occur. . Zn (OH)
Z-attached Zn S: The relationship between the amount of Zn(OH)2 deposited on the Ag phosphor (including the amount of 0 deposited) and the dispersibility of the phosphor is shown in FIG.
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８０
ｇ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。In FIG. 3, dispersibility (vertical axis) is represented by sedimentation volume. The value of this sedimentation volume is calculated by adding 5g of the phosphor sample to 80% of the polyvinyl alcohol aqueous solution containing ammonium dichromate.
g, and allowed to settle in a sedimentation tube for 24 hours, then the volume was read and converted to volume per 1 g. The larger the settling volume value, the worse the dispersibility.
第３図から明らかなように、分散性はＺｎ （０Ｈ）
ｚ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）ｚ付
着量が０．５重量部よりも多くなるとＺｎ（ＯＨ）ｚ付
着量が増加するに従っ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
ネーションの点から本発明におけるＺｎ （ＯＨ）ｚ
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
への界面活性剤の添加あるいはその界面活性剤を選択す
る等の手段によっである程度改良することができる。As is clear from Figure 3, the dispersibility of Zn (0H)
Up to about 0.5 parts by weight, the Zn(OH)2 adhesion amount is almost the same as when the Zn(OH)2 adhesion amount is 0, but when the Zn(OH)z adhesion amount exceeds 0.5 parts by weight, the Zn(OH) ) It can be seen that as the amount of z adhesion increases, it becomes worse. As mentioned above, Zn(OH)z in the present invention is
Although the upper limit of the amount of zn(OH)2 attached is set at 0.7, taking into consideration the dispersibility, it is more preferable that the amount of zn(OH)2 attached is 0.5 part 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.
本発明によっ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。The phosphor slurry obtained by the present invention significantly increases exposure sensitivity.
第４図はＺｎ （ＯＨ）２付着Ｚｎ Ｓ ：Ａｇ蛍光
体（付着量０も含む）のＺｎ （ＯＨ）ｚ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（
２３０μＴｒＬ）のストライブ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）ｚ付着量が約１．２重量部までは
Ｚｎ 、（ＯＨ）ｚ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ブを得ることができる。すなわち
、Ｚｎ（ＯＨ）ｚ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。従ってこのように
露光感度が向上した蛍光体スラリーを用いることによっ
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）ｚ付着量
０の場合と同じにする時には、同じストライブを得るの
に光源光量を減らすことができ、従って光源寿命を延ば
すことができる。Figure 4 shows the Zn (OH)z adhesion amount of Zn (OH)2 adhesion Zn S :Ag phosphor (including 0 adhesion amount), and
Using the phosphor slurry using the phosphor, a certain width (
230 μTrL) 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)z 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)z deposited is 0. Can be done. That is, when the amount of Zn(OH)z deposited is about 1.2 parts by weight, which is more than 0 parts by weight, the exposure sensitivity of the phosphor slurry is improved. In particular, when the amount of Zn(OH)2 deposited is 0.05 to 1.0 parts by weight, the exposure sensitivity is significantly improved. Therefore, by using a phosphor slurry with improved exposure sensitivity as described above, exposure time can be shortened and work efficiency can be increased. Furthermore, when the exposure time is the same as in the case where the amount of Zn(OH)z deposited is 0, the amount of light from the light source can be reduced to obtain the same stripe, and therefore the life of the light source can be extended.
上述のように適当量のＺｎ（ＯＨ）ｚ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）ｚあるいは一部溶解したＺ
ｎ”十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。As mentioned above, it is not clear why the exposure sensitivity of a phosphor slurry using a phosphor to which an appropriate amount of Zn(OH)z is attached is improved;
It is thought that this is because n'' acts as a catalyst in the phosphor slurry and promotes photopolymerization of the photosensitive resin.
以上本発明の効果をＺｎ Ｓ ： 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ョン用
蛍光用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、分散剤処理を行なったカラーテレビジョン
用蛍光体あるいは分散剤処理を行なってないカラーテレ
ビジョ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。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 fluorescent materials for color televisions. Furthermore, it was 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.
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ョ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って、その
工業的利用価値は、非常に大きなものである。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.
次に実施例によって本発明を説明する。Next, the present invention will be explained by examples.
実施例ｌ
ＺｎＳ：Ｃｕ、Ａ５１蛍光体とＺｎＳ：Ａｕ５Ａ免蛍光
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１０００９を２！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ＡＳＳｔ ｏ
２２０重量％含有）を１５ｇ加えて攪拌し、さらに硫酸
亜鉛の１０％水溶液９０ｇを添加した。１０分間攪拌後
攪拌を止めて蛍光体を沈降させ、上澄み液をデカンテー
ションにて除去した。その後蛍光体を５９．、の純水で
２回水洗した。このようにして５ｉＯｚによる表面処理
を完了し、ＳｉＯ２が付着した蛍光体を得た。Example 1 Green-emitting component phosphor 10009, which is a mixture of ZnS:Cu, A51 phosphor and ZnS:Au5A non-phosphor at a weight ratio of 7:3, was prepared by 2!2. was suspended in pure water. Add water glass (Oka Seal ASSt o manufactured by Tokyo Ohka Co., Ltd.) to this suspension.
220% by weight) was added and stirred, and further 90g 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. After that, 59. It was washed twice with pure water. In this way, the surface treatment with 5iOz was completed, and a phosphor to which SiO2 was attached was obtained.
次に上述のようにして得た５ｉ０２が付着した蛍光体を
２免の純水中に懸濁させ、この懸濁液に硫酸亜鉛の１０
％水溶液２８９を加え、その後攪拌しなからＮａＯＨ水
溶液で懸濁液ＯＰＨ値を１０．０に調整した。ＰＨ調整
後さらに５分間攪拌を続けた。攪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ョンにて除去し、さ
らに蛍光体を５９．、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メツシユの篩で篩った。Next, the phosphor to which 5i02 was attached, obtained as described above, was suspended in 2 ml of pure water, and this suspension was added with 10 ml of zinc sulfate.
% aqueous solution was added, and then, without stirring, the OPH value of the suspension was adjusted to 10.0 with an aqueous NaOH 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 removed by 59. , and washed once with pure water. Thereafter, the phosphor was dehydrated by suction and dried at 150° C. for 3 hours. After drying, the phosphor was sieved through a 250 mesh sieve.
上述のように５１０２による表面処理および２ｎ（ＯＨ
）ｚによる表面処理を行なった蛍光体には、Ｓｉｎｇと
Ｚｎ（ＯＨ）ｚが付着しており、Ｚｎ （ＯＨ）ｚの
付着量は混合縁色発光成分蛍光体１００重量部に対して
０．１４重量部であった。Surface treatment with 5102 and 2n(OH
) Z has Sing and Zn(OH)z attached to the phosphor surface-treated with Zn(OH)z, and the amount of Zn(OH)z attached is 0.00 parts by weight per 100 parts by weight of the mixed edge color emitting component phosphor. It was 14 parts by weight.
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ョン）および露光感度（露光時
間）を調べた。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 mixing (haze and cross-contamination) and exposure sensitivity (exposure time) were investigated.
その結果を第１表に上述の５ＩＯ２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
かった混合蛍光体の場合（第１表括弧内の値）と比較し
て示す。なおりロスコンタミネーションは青色発光成分
蛍光体としてＺｎ Ｓ ： Ａｇ蛍光体、赤色発光成分
蛍光体としてＹ２ｏ２ｓ二Ｅｕ蛍光体を用い［いずれも
Ｚｎ（ＯＨ）ｚ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ョン（青色出
力／緑色出力）および後塗布Ｙ２０□Ｓ ： Ｅｕ赤色
発光成分蛍光体とのクロスコンタミネーション（赤色出
力／緑色出力）を測定した。The results are shown in Table 1 in comparison with the case of a mixed phosphor (values in parentheses in Table 1) which was subjected to surface treatment only with 5IO2 and not surface treated with Zn(OH)2. For Naori loss contamination, ZnS:Ag phosphor was used as the blue-emitting component phosphor, Y2O2s2Eu phosphor was used as the red-emitting component phosphor [both Zn(OH)z untreated], and green, blue and red light-emitting components were used. Post-coating ZnS: cross-contamination with Ag blue-emitting component phosphor (blue output/green output) and post-coating Y20□S: cross-contamination with Eu red-emitting component phosphor (when coating in the order of component phosphors) red output/green output) was measured.
第１表から明らかなように、Ｚｎ （ＯＨ）ｚによる
表面処理を行なった蛍光体は、Ｚｎ （ＯＨ）２によ
る表面処理を行なわなかっ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
った。As is clear from Table 1, the phosphor whose surface was treated with Zn (OH)z had less color mixture in the phosphor film than the phosphor whose surface was not treated with Zn (OH)2. The exposure sensitivity of the slurry was high.
実施例２
Ｚｎ Ｓ ：Ａｕ５ＣｕＳＡ９Ｊ緑色発光成分蛍光体１
０００ ｇを２９Ｊの純水中に懸濁させ、この懸濁液に
塩化亜鉛の２０％水溶液２３．８ｇを加え、その後攪拌
しなからＮＨ，ＯＨ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分間攪拌を続けた。Example 2 ZnS:Au5CuSA9J green light emitting component phosphor 1
000 g was suspended in 29 J of pure water, 23.8 g of a 20% aqueous solution of zinc chloride was added to this suspension, and then, without stirring, the pH value of the suspension was adjusted to 8.0 with an NH,OH aqueous solution. Adjusted to. After adjusting the pH, stirring was continued for an additional 5 minutes.
攪拌を止め蛍光体を沈降させた後、上澄み液をデカンテ
ーションにて除去し、さらに蛍光体を５免の純水で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メツシユの篩で篩っ
た。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 5 ml of pure water. Thereafter, the phosphor was dehydrated by suction and dried at 100° C. for 8 hours. After drying, the phosphor was sieved through a 250 mesh sieve.
上述のようにしてＺｎ （ＯＨ）ｚによる表面処理を
行なったＺｎＳ：Ａｕ５Ｃｕ、Ａえ蛍光体には、Ｚｎ
（ＯＨ）ｚが付着しており、Ｚｎ （ＯＨ）２の付
着量はＺｎ Ｓ：Ａｕ５ＣｕＳＡ、Ｑ、蛍光体１００重
量部に対して０．２６重量部であった。The ZnS:Au5Cu,A phosphor surface-treated with Zn (OH) as described above contains Zn.
(OH)z was attached, and the amount of Zn(OH)2 attached was 0.26 parts by weight per 100 parts by weight of ZnS:Au5CuSA,Q, phosphor.
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ョン）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）ｚに
よる表面処理を行なわなかったＺ ｎ Ｓ ： Ａ ｕ
１Ｃｕ ｓ Ａ見蛍光体の場合（第１表括弧内の値）
と比較して示す。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 to prevent color mixing (haze and cross contamination). Exposure sensitivity (exposure time)
I looked into it. The results are shown in Table 1 for Z n S : A u
In the case of 1Cu s A phosphor (values in parentheses in Table 1)
A comparison is shown below.
なおりロスコンタミネーションは青色発光成分蛍光体と
してＺｎ Ｓ ： Ａｇ蛍光体、赤色発光成分蛍光体と
してＹ２０２ Ｓ ： Ｅｕ蛍光体を用い［いずれもＺ
ｎ（ＯＨ）ｚ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後塗布Ｚｎ Ｓ ： Ａｇ
青色発光成分蛍光体とのクロスコンタミネーション（青
色出力／緑色出力）および後塗布Ｙ２０２ Ｓ ： Ｅ
ｕ赤色発光成分蛍光体とのクロスコンタミネーション（
赤色出力／緑色出力）を測定した。For Naori loss contamination, ZnS:Ag phosphor was used as the blue light-emitting component phosphor, and Y202S:Eu phosphor was used as the red light-emitting component phosphor [both Z
Post-coating ZnS: Ag
Cross-contamination with blue-emitting component phosphor (blue output/green output) and post-coating Y202 S: E
uCross contamination with red emitting component phosphor (
red output/green output) was measured.
第１表から明らかなように、Ｚｎ（ＯＨ）ｚによる表面
処理を行なったＺｎ Ｓ：ＡｕＸＣｕ、Ａ２蛍光体は、
この処理を行なわなかったＺｎＳ：Ａ ｕ ｓ Ｃｕ
ＳＡ ９１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った。As is clear from Table 1, the ZnS:AuXCu, A2 phosphor whose surface was treated with Zn(OH)z is
ZnS that was not subjected to this treatment: A u s Cu
Less color mixing in the phosphor film than SA 91 phosphor,
Furthermore, the exposure sensitivity of the phosphor slurry was high.
実施例３
Ｚｎ Ｓ ： Ａｇ青色発光成分蛍光体１０００ｇを２
免の純水中に懸濁させ、実施例１と同様にして５ｉ０２
による表面処理を行ない、ＳｉＯ２が付着した蛍光体を
得た。Example 3 ZnS: 1000g of Ag blue-emitting component phosphor was
5i02 was suspended in pure water and treated in the same manner as in Example 1.
A phosphor to which SiO2 was attached was obtained.
次に上述のようにして得たＳｉＯ□が付着した蛍光体を
２免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、その後攪拌しなからＮａＯ
Ｈ水溶液で懸濁液のＰＨ値を９，０に調製した。ＰＨ調
整後さらに５分間攪拌を続けた。Next, the phosphor with SiO
Add 18.7 g of % aqueous solution, then add NaO without stirring.
The pH value of the suspension was adjusted to 9.0 with an aqueous H solution. After adjusting the pH, stirring was continued for an additional 5 minutes.
攪拌を止め蛍光体を沈降させた後、上澄み液をデカンテ
ーションにて除去し、さらに５９Ｊ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メツシユの篩で篩った。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 59 J of pure water. Thereafter, the phosphor was dehydrated by suction and dried at 200° C. for 3 hours. After drying, the phosphor was sieved through a 250 mesh sieve.
上述のようにして５ＩＯ２による表面処理およびＺｎ
（ＯＨ）ｚによる表面処理を行なったＺｎＳ：Ａｇ蛍
光体には、５ＩＯ２とＺｎ （ＯＨ）ｚが付着してお
り、Ｚｎ（ＯＨ）ｚの付着量はＺｎＳ：Ａｇ蛍光体１０
０重量部に対して０．０８重量部であった。Surface treatment with 5IO2 and Zn as described above
5IO2 and Zn (OH)z are attached to the ZnS:Ag phosphor that has been surface-treated with (OH)z, and the amount of Zn(OH)z attached is 10% of the ZnS:Ag phosphor.
The amount was 0.08 parts by weight compared to 0 parts by weight.
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ョン）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８１０２による表
面処理のみを行ない、Ｚｎ （ＯＨ）２による表面処
理を行なわなかったＺｎ Ｓ ： Ａｇ蛍光体の場合（
第１表括弧内の値）と比較して示す。なおりロスコンタ
ミネーションは緑色発光成分蛍光体としてＺｎＳ：Ｃｕ
、ＡＱ、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：Ｃｕ５Ａλ緑色発光成分
蛍光体とのクロスコンタミネーション（青色出力／緑色
出力）および後塗布Ｙ２゜２Ｓ：Ｅｕ赤色発光成分蛍光
体とのクロスコンタミネーション（赤色出力／青色出力
）をＣｊ定した。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 to prevent color mixing (haze and cross contamination). Exposure sensitivity (exposure time)
I looked into it. The results are shown in Table 1. In the case of ZnS:Ag phosphor which was subjected to surface treatment with 8102 described above but not with Zn(OH)2 (
Table 1 (values in parentheses). Naori loss contamination is caused by using ZnS:Cu as a green emitting component phosphor.
, AQ, phosphor, Y2O2S as red emitting component phosphor
: Using Eu phosphor [both Zn(OH)2
Untreated], pre-coating ZnS:Cu5Aλ cross-contamination with green-emitting component phosphor (blue output/green output) when green, blue and red emitting component phosphors are applied in order and post-coating Y2゜2S:Eu red Cross contamination (red output/blue output) with the luminescent component phosphor was determined as Cj.
第１表から明らかなように、Ｚｎ（ＯＨ）ｚによる表面
処理を行なったＺｎ Ｓ ： Ａｇ蛍光体は、この処理
を行なわなかったＺｎ Ｓ ： 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
度が高かった。As is clear from Table 1, the ZnS:Ag phosphor that has been surface-treated with Zn(OH)z has less color mixture in the phosphor film than the ZnS:Ag phosphor that has not been subjected to this treatment. The exposure sensitivity of the phosphor slurry was high.
実施例４
ＺｎＳ：Ａｇ、Ａ９Ｊ青色発光蛍光体１０００ｇを２免
の純水中に懸濁させ、この懸濁液に硝酸亜鉛の２０％水
溶液８７９を加え、その後攪拌しながら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分間攪拌を続けた。攪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ョンにて除去し、さらに蛍
光体を５北の純水で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メツシユの篩で篩った。Example 4 1000 g of ZnS:Ag, A9J blue light-emitting phosphor was suspended in 200 g of pure water, 20% aqueous solution of zinc nitrate 879 was added to this suspension, and then the suspension was added with a KOH aqueous solution while stirring. The pH value was adjusted to 11.0. 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 phosphor was further washed once with 5Kita pure water. Thereafter, the phosphor was dehydrated by suction and dried at 150° C. for 3 hours. After drying, the phosphor was sieved through a 250 mesh sieve.
上述のようにしてＺｎ （ＯＨ）２による表面処理を
行なったＺｎＳ：Ａｇ、Ａ９Ｊ蛍光体には、Ｚｎ（ＯＨ
）ｚが付着しており、そのＺｎ （ＯＨ）２付着量は
ＺｎＳ：Ａｇ、ＡＱ、蛍光体１００重量部に対して０，
５１重量部であった。The ZnS:Ag, A9J phosphor that was surface-treated with Zn(OH)2 as described above was coated with Zn(OH)2.
)z is attached, and the amount of Zn (OH)2 attached is 0,
It was 51 parts by weight.
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ョン）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）ｚに
よる表面処理を行なわなかったＺｎＳ：Ａｇ５Ａ免蛍光
体の場合（第１表括弧内の値）と比較して示す。なおり
ロスコンタミネーションは緑色発光成分蛍光体としてＺ
ｎＳ：Ｃｕ、Ａ９Ｊ蛍光体、赤色発光成分蛍光体として
ＹＺ ０２ Ｓ ： Ｅｕ蛍光体を用い［いずれもＺｎ
（ＯＨ）ｚ未処理コ、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Ｚｎ Ｓ ： Ｃｕ
ｓ ＡＱＩ緑色発光成分蛍光体とのクロスコンタミネー
ション（青色出力／緑色出力）および後塗布Ｙ２０２
Ｓ ： Ｅｕ赤色発光成分蛍光体とのクロスコンタミネ
ーション（赤色出力／青色出力）を測定した。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 to prevent color mixing (haze and cross contamination). Exposure sensitivity (exposure time)
I looked into it. The results are shown in Table 1 in comparison with the case of ZnS:Ag5A non-fluorescent material which was not subjected to the above-mentioned surface treatment with Zn(OH)z (values in parentheses in Table 1). Naori loss contamination is caused by Z as a green emitting component phosphor.
nS: Cu, A9J phosphor, YZ 02 S: Eu phosphor was used as the red light emitting component phosphor [both Zn
Pre-coating when (OH)z untreated co, green, blue and red emitting component phosphors are applied in this order ZnS: Cu
s Cross contamination with AQI green emitting component phosphor (blue output/green output) and post-coating Y202
S: Cross contamination (red output/blue output) with Eu red light emitting component phosphor was measured.
第１表から明らかなように、Ｚｎ（ＯＨ）ｚによる表面
処理を行なったＺｎＳ：Ａｇ、Ａ、Ｑ、蛍光体は、この
処理を行なわなかったＺｎＳ：Ａｇ。As is clear from Table 1, ZnS:Ag, A, and Q were subjected to surface treatment with Zn(OH)z, and ZnS:Ag was not subjected to this treatment.
Ａ９Ｊ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った。There was less color mixing in the phosphor film than with the A9J phosphor, and the exposure sensitivity of the phosphor slurry was higher.
実施例５
ＹＺ ０２ Ｓ ： Ｅｕ赤色発光成分蛍光体１０００
ｇを２９Ｊの純水中に懸濁させ、この懸濁液に硫酸亜
鉛の１０％水溶液１１２９を加え、その後攪拌しなから
ＮＨ，ＯＨ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分間攪拌を続けた。攪拌を止め蛍
光体を沈降させた後、上澄み液をデカンテーションにて
除去し、さらに蛍光体を５！２．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メツシユの篩で篩った。Example 5 YZ 02 S: Eu red light emitting component phosphor 1000
g was suspended in 29 J of pure water, a 10% aqueous solution of zinc sulfate 1129 was added to this suspension, and the pH value of the suspension was adjusted to 9.0 with an NH,OH aqueous solution without 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 removed by 5!2. Washed three times with pure water. Thereafter, the phosphor was dehydrated by suction and dried at 130° C. for 6 hours. After drying, the phosphor was sieved through a 250 mesh sieve.
上述のようにしてＺｎ（ＯＨ）ｚによる表面処理を行な
ったＹＺ０゜Ｓ ： Ｅｕ蛍光体には、Ｚｎ（ＯＨ）ｚ
が付着しており、そのＺｎ （ＯＨ）ｚ付着量はＹＺ
０２ Ｓ ： Ｅｕ蛍光体１００重量部に対して０．
５７重量部であった。YZ0°S surface treated with Zn(OH) as described above: Eu phosphor has Zn(OH)
is attached, and the amount of Zn (OH)z attached is YZ
02S: 0.0% per 100 parts by weight of Eu phosphor.
It was 57 parts by weight.
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ョン）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）
ｚによる表面処理を行なわなかったＹＺ ０２ Ｓ ：
Ｅｕ蛍光体の場合（第１表括弧内の値）と比較して示
す。なおりロスコンタミネーショ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Ｚ ｎ Ｓ ： Ｃｕ ｓ Ａ ９１蛍光体［いずれ
もＺｎ （ＯＨ）ｚ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Ｚｎ Ｓ
： Ｃｕ ５Ａ９Ｊ緑色発光成分蛍光体とのクロスコン
タミネーション（赤色出力／緑色出力）および前塗布Ｚ
ｎＳ：Ａｇ青色発光成分蛍光体とのクロスコンタミネー
ション（赤色出力／青色出力）を測定した。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 to prevent color mixing (haze and cross contamination). Exposure sensitivity (exposure time)
I looked into it. The results are shown in Table 1.
YZ 02 S without surface treatment by Z:
A comparison with the case of Eu phosphor (values in parentheses in Table 1) is shown. As for loss contamination, ZnS:Ag phosphor was used as the blue-emitting component phosphor, ZnS:CusA 91 phosphor was used as the green-emitting component phosphor [both untreated with Zn(OH)z], green, blue and Pre-coating Zn S when applied in the order of red emitting component phosphor
: Cross contamination with Cu 5A9J green emitting component phosphor (red output/green output) and pre-coating Z
Cross contamination (red output/blue output) with the nS:Ag blue-emitting component phosphor was measured.
第１表から明らかなように、Ｚｎ（ＯＨ）ｚによる表面
処理を行なったＹＺ ０２ Ｓ ： Ｅｕ蛍光体は、こ
の処理を行なわなかったＹＺ ０２ Ｓ ： 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った。As is clear from Table 1, the YZ 02 S:Eu phosphor whose surface was treated with Zn(OH)z has less color mixture in the phosphor film than the YZ 02 S: Eu-phosphor which was not subjected to this treatment. Moreover, the exposure sensitivity of the phosphor slurry was high.
実施例６
ベんがら赤色顔料粒子材Ｙ２０２ Ｓ ： Ｅｕ赤色発
光蛍光体１０００ｇを２９Ｌの純水中に懸濁させ、実施
例１と同様にして５１０２による表面処理を行ない、Ｓ
ｉＯ２が付着した蛍光体を得た。Example 6 Red red pigment particle material Y202S: 1000g of Eu red light-emitting phosphor was suspended in 29L of pure water, and the surface treatment with 5102 was performed in the same manner as in Example 1.
A phosphor with iO2 attached was obtained.
次に上述のようにして得たＳ１０□が付着した蛍光体を
２免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、その後攪拌しなから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分間攪拌を続けた。攪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ョンにて除去し、さら
に５９．、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２
５０メツシユの篩で篩った。Next, the phosphor with S10
% aqueous solution was added thereto, and then, without stirring, the pH value of the suspension was adjusted to 8.0 with an aqueous NaOH solution. 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 further 59. It was washed twice with pure water. Thereafter, the phosphor was dehydrated by suction and dried at 200° C. for 3 hours. After drying, add 2 phosphors
Sieved through a 50 mesh sieve.
上述のようにしてＳｉｎ、による表面処理およびＺｎ
（ＯＨ）２による表面処理を行なったべんから赤色顔
料粒子付Ｙ２０□ＳＥＥυ蛍光体には、ＳｉＯ２とＺｎ
（ＯＨ）ｚ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材ＹＺ ０２ Ｓ ： Ｅ
ｕ蛍光体１００重量部に対して０．３０重量部であった
。Surface treatment with Sin and Zn as described above
The Y20□SEEυ phosphor with red pigment particles has been surface-treated with (OH)2 and contains SiO2 and Zn.
(OH)z is attached, and the amount of Zn(OH)2 attached is red pigment particle material YZ 02 S: E
The amount was 0.30 parts by weight per 100 parts by weight of the u-phosphor.
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ョン）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８１０２による表
面処理のみを行ない、Ｚｎ （ＯＨ）ｚによる表面処
理を行なわなかったべんがら赤色顔料粒子材ＹｚＯ２Ｓ
：ＥＵ蛍光体の場合（第１表括弧内の値）と比較して示
す。なおりロスコンタミネーショ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：Ｃｕ５ＡＱ、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、Ａ、
Ｑ、緑色発光成分蛍光体とのクロスコンタミネーション
（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ョン（赤色出
力／青色出力）を測定した。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 to prevent color mixing (haze and cross contamination). Exposure sensitivity (exposure time)
I looked into it. The results are shown in Table 1 for the red pigment particle material YzO2S, which was subjected to surface treatment only with 8102 described above and without surface treatment with Zn (OH)z.
: Shown in comparison with the case of EU phosphor (values in parentheses in Table 1). For Naori loss contamination, ZnS:Ag phosphor was used as the blue-emitting component phosphor, and ZnS:Cu5AQ and phosphor were used as the green-emitting component phosphor [both Zn
(OH)2 untreated], pre-coated ZnS when green, blue and red emitting component phosphors are applied in this order: Cu, A,
Q. Cross-contamination with green-emitting component phosphor (red output/green output) and cross-contamination with pre-coated ZnS:Ag blue-emitting component phosphor (red output/blue output) were measured.
第１表から明らかなように、Ｚｎ （ＯＨ）２による
表面処理を行なったべんから赤色顔料粒子材Ｙ２０２
Ｓ ： Ｅｕ蛍光体は、この処理を行なわなかったべん
がら赤色顔料粒子材Ｙ２０２ Ｓ ： 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
露光感度が高かった。As is clear from Table 1, the red pigment particle material Y202 was surface-treated with Zn(OH)2.
The S:Eu phosphor had less color mixing in the phosphor film than the red pigment particle material Y202 S:Eu phosphor that was not subjected to this treatment, and the exposure sensitivity of the phosphor slurry was higher.
第１図はＺｎ （ＯＨ）２付着Ｚｎ Ｓ ： Ａｇ蛍
光体（付着量０も含む）のＺｎ（ＯＨ）ｚ付着量とへイ
ズとの関係を示すグラフである。
第２図−（Ａ）はＺｎ（ＯＨ）ｚ付着Ｚｎ Ｓ ：Ａｇ
蛍光体（付着量Ｏも含む）のＺｎ （ＯＨ）ｚ付着量
と、その蛍光体スラリーの前塗布ＺｎＳ：ＣＯ，Ａ９Ｊ
緑色発光成分蛍光体とのクロスコンタミネーションの関
係を示すグラフである。
第２図−（Ｂ）はＺｎ（ＯＨ）ｚ付着ＺｎＳ：Ａｇ蛍光
体（付着量Ｏも含む）のＺｎ（ＯＨ）ｚ付着量と、その
蛍光体スラリーの後塗布Ｙ２０ｚＳ ： Ｅｕ赤色発光
成分蛍光体とのクロスコンタミネーションの関係を示す
グラフである。
第３図はＺｎ （ＯＨ）ｚ付着Ｚｎ Ｓ ： Ａｇ蛍
光体（付着ｆｆ１Ｏも含む）のＺｎ （ＯＨ）ｚ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Ｚｎ Ｓ ： Ａｇ蛍
光体（付着量０も含む）のＺｎ（ＯＨ）ｚ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（２
３０μｍ）のストライブを形成する時の露光時間との関
係を示すグラフである。
第 １ 図
ｚｎ（ＯＨ）２ＪｔＪｌ （１１１５１１／ＺｎＳ：
Ａｇ ＋ＯＯｔ！仰）９′）４’７
第２図（ハ）
ｚｎ（ｏＨ）ｚｒｊ、ｔｉ（ｆ１ｇ＋＋／ｚｎｓ：Ａｇ
１ｏｏｉＬ’ｇρ）第２図（Ｂ）
’ｚｎ（ＯＨ）２Ｊｊ４１０ｔ１ｇｐ／ ＺｎＳ：Ａｇ
＋ＯＯ！ ｌ ｇｌ））第３図FIG. 1 is a graph showing the relationship between the amount of Zn(OH)z deposited and the haze of Zn(OH)2-deposited ZnS:Ag phosphor (including a deposited amount of 0). Figure 2 - (A) shows Zn(OH)z adhesion ZnS:Ag
Zn(OH)z adhesion amount of phosphor (including adhesion amount O) and pre-coating of the phosphor slurry ZnS:CO,A9J
It is a graph showing the relationship of cross-contamination with a green light-emitting component phosphor. Figure 2-(B) shows the Zn(OH)z adhesion amount of the Zn(OH)z-adhered ZnS:Ag phosphor (including the adhesion amount O) and the post-coating of the phosphor slurry Y20zS:Eu red emitting component fluorescence It is a graph showing the relationship of cross-contamination with the body. FIG. 3 is a graph showing the relationship between the amount of Zn (OH)z attached to Zn (OH)z attached Zn S :Ag phosphor (including attached ff1O) and the dispersibility of the phosphor. Figure 4 shows the Zn(OH)z adhesion amount of Zn(OH)2 adhering ZnS:Ag phosphor (including 0 adhesion amount) and the Zn(OH)z adhesion amount using the phosphor slurry using the phosphor.
30 is a graph showing the relationship with exposure time when forming stripes (30 μm). Figure 1 zn(OH)2JtJl (111511/ZnS:
Ag+OOt! 9') 4'7 Figure 2 (c) zn(oH)zrj,ti(f1g++/zns:Ag
1ooiL'gρ) Figure 2 (B) 'zn(OH)2Jj410t1gp/ ZnS:Ag
+OO! l gl)) Figure 3
Claims (7)
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。(1) A phosphor slurry for making a phosphor film, which is made of 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.
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。(2) The phosphor slurry for producing a phosphor film according to claim 1, wherein the dichromate is ammonium dichromate.
、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。(3) A patent claim 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). A phosphor slurry for forming a phosphor film according to the range 1 or 2.
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。(4) Claims 1 to 3, characterized in that the alkali hydroxide is at least one selected from the group consisting of sodium hydroxide, potassium hydroxide, and ammonium hydroxide. The phosphor slurry for forming a phosphor film according to any one of the items.
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。(5) Any one of claims 1 to 4, characterized in that a dispersant is also used in the surface treatment.
A phosphor slurry for making a phosphor film as described in .
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。(6) The phosphor slurry for producing a phosphor film according to claim 5, wherein the dispersant is silicon dioxide.
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。(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 true JPH01213387A (en) | 1989-08-28 |
| JPH037712B2 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) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5310504A (en) * | 1991-08-21 | 1994-05-10 | Samsung Electron Devices Co., Ltd. | Phosphor slurry composition for color Braun tubes |
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 |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5310504A (en) * | 1991-08-21 | 1994-05-10 | Samsung Electron Devices Co., Ltd. | Phosphor slurry composition for color Braun tubes |
| US5322707A (en) * | 1991-08-21 | 1994-06-21 | Samsung Electron Devices Co. Ltd. | Method of forming a fluorescent screen |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH037712B2 (en) | 1991-02-04 |
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