JPS6154076B2 - - Google Patents
Info
- Publication number
- JPS6154076B2 JPS6154076B2 JP5082378A JP5082378A JPS6154076B2 JP S6154076 B2 JPS6154076 B2 JP S6154076B2 JP 5082378 A JP5082378 A JP 5082378A JP 5082378 A JP5082378 A JP 5082378A JP S6154076 B2 JPS6154076 B2 JP S6154076B2
- Authority
- JP
- Japan
- Prior art keywords
- phosphor
- particles
- pigment particles
- pigment
- slurry
- 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
Links
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 111
- 239000002245 particle Substances 0.000 claims description 111
- 239000000049 pigment Substances 0.000 claims description 50
- 239000002002 slurry Substances 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 28
- 239000012736 aqueous medium Substances 0.000 claims description 14
- 239000011248 coating agent Substances 0.000 claims description 13
- 239000010408 film Substances 0.000 description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 238000000576 coating method Methods 0.000 description 8
- 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 8
- 108010010803 Gelatin Proteins 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 7
- 229920000159 gelatin Polymers 0.000 description 7
- 239000008273 gelatin Substances 0.000 description 7
- 235000019322 gelatine Nutrition 0.000 description 7
- 235000011852 gelatine desserts Nutrition 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 239000001055 blue pigment Substances 0.000 description 6
- 238000004528 spin coating Methods 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- JOSWYUNQBRPBDN-UHFFFAOYSA-P ammonium dichromate Chemical compound [NH4+].[NH4+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O JOSWYUNQBRPBDN-UHFFFAOYSA-P 0.000 description 4
- 238000007796 conventional method Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- 239000001054 red pigment Substances 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- -1 ethyleneimino Chemical group 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000001302 tertiary amino group Chemical group 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 1
- DPBJAVGHACCNRL-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate Chemical compound CN(C)CCOC(=O)C=C DPBJAVGHACCNRL-UHFFFAOYSA-N 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical group C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- 240000004160 Capsicum annuum Species 0.000 description 1
- 235000008534 Capsicum annuum var annuum Nutrition 0.000 description 1
- 235000007862 Capsicum baccatum Nutrition 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- VCUFZILGIRCDQQ-KRWDZBQOSA-N N-[[(5S)-2-oxo-3-(2-oxo-3H-1,3-benzoxazol-6-yl)-1,3-oxazolidin-5-yl]methyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C1O[C@H](CN1C1=CC2=C(NC(O2)=O)C=C1)CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F VCUFZILGIRCDQQ-KRWDZBQOSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- IRERQBUNZFJFGC-UHFFFAOYSA-L azure blue Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[S-]S[S-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] IRERQBUNZFJFGC-UHFFFAOYSA-L 0.000 description 1
- ITHZDDVSAWDQPZ-UHFFFAOYSA-L barium acetate Chemical compound [Ba+2].CC([O-])=O.CC([O-])=O ITHZDDVSAWDQPZ-UHFFFAOYSA-L 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical compound [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 description 1
- 239000001728 capsicum frutescens Substances 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000001493 electron microscopy Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000001056 green pigment Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 108091008695 photoreceptors Proteins 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 239000000725 suspension Substances 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
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Landscapes
- Luminescent Compositions (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
Description
【発明の詳細な説明】
本発明は螢光体スラリーの調製方法に関する。
更に詳しくは本発明は顔料粒子を混入させること
によつて螢光膜の反射率を低下させ、画像のコン
トラストを向上させた高コントラスト螢光膜を作
成するための螢光体スラリーの調製方法に関す
る。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for preparing a phosphor slurry.
More specifically, the present invention relates to a method for preparing a phosphor slurry for creating a high-contrast phosphor film in which the reflectance of the phosphor film is reduced and the image contrast is improved by incorporating pigment particles. .
周知のように、螢光体粒子の周囲にその螢光体
粒子の発光色以外の可視光を吸収する顔料粒子が
存在する様に作られた螢光膜は、外光の反射率が
低下し、このために螢光体粒子のみからなる螢光
膜に比べて画像のコントラストが著しく向上し、
また発光輝度の低下が比較的少ない。この方法に
よつて画像のコントラストを改善した螢光膜、す
なわち高コントラスト螢光膜は、主としてカラー
テレビジヨンブラウン管で実用化されている（特
開昭50−56146号参照）。 As is well known, a phosphor film made in such a way that pigment particles that absorb visible light other than the emission color of the phosphor particles are present around the phosphor particles has a reduced reflectance of external light. Therefore, the contrast of the image is significantly improved compared to a phosphor film made only of phosphor particles.
Further, the reduction in luminance of light emission is relatively small. Fluorescent films with improved image contrast by this method, that is, high-contrast fluorescent films, have been put to practical use mainly in color television cathode ray tubes (see Japanese Patent Application Laid-Open No. 56146/1983).
カラーテレビジヨンブラウン管においては、高
コントラスト螢光膜を作成する方法として、現在
以下に述べる３つの方法が採用されている。 In color television cathode ray tubes, the following three methods are currently employed to create high contrast fluorescent films.
第１の方法は、螢光膜作成に使用する螢光体粒
子表面に、あらかじめ接着物質によつて顔料粒子
を強固に付着させて顔料付着螢光体を得、この顔
料付着螢光体を用いて通常の方法で螢光体スラリ
ーを調製し、これを従来の方法でフエースプレー
ト上に塗布し螢光膜とする方法である（特開昭50
−56146号参照）。この方法は、通常の螢光体のか
わりに顔料付着螢光体を用いる事以外は従来のカ
ラーテレビジヨンブラウン管螢光膜作成方法と何
ら変るところがなく、優れた方法としてカラーテ
レビジヨンブラウン管の高コントラスト螢光膜作
成方法として広く実用されている。しかしなが
ら、この方法は螢光体粒子表面にあらかじめ顔料
粒子を付着せしめる工程を必要とし、従つて螢光
膜作成がコスト高になるという欠点を有してい
る。 The first method is to obtain a pigment-attached phosphor by firmly adhering pigment particles to the surface of the phosphor particles used for making a fluorescent film using an adhesive substance, and then use this pigment-attached phosphor to obtain a pigment-attached phosphor. In this method, a phosphor slurry is prepared using a conventional method, and this is applied onto a face plate using a conventional method to form a phosphor film (Japanese Patent Laid-Open No.
-Refer to No. 56146). This method is no different from the conventional method for producing a color television cathode ray tube phosphor film, except that a pigment-coated phosphor is used instead of a normal phosphor. It is widely used as a method for producing fluorescent films. However, this method requires a step of adhering pigment particles to the surface of the phosphor particles in advance, and therefore has the disadvantage that the production of the phosphor film is expensive.
第２の方法は、顔料スラリーを用いてあらかじ
めフエースプレート上に顔料粒子層を形成し、こ
の上に螢光体スラリーを用いて螢光体粒子層を形
成させる方法である（特開昭48−46266号参照）。
この方法は螢光膜作成に要する時間が通常の螢光
膜作成に要する時間の２倍以上となるという欠点
を有する。 The second method is to form a pigment particle layer on the face plate in advance using a pigment slurry, and then form a phosphor particle layer on top of this using a phosphor slurry (Japanese Patent Laid-Open No. 1983-1992-1). (See No. 46266).
This method has the disadvantage that the time required to create a fluorescent film is more than twice the time required to create a normal fluorescent film.
第３の方法は、螢光体粒子と共に顔料粒子を感
光性水溶液中に分散させて螢光体スラリーを調製
し、この螢光体スラリーを従来の方法でフエース
プレート上に塗布し螢光膜とする方法である。こ
の方法によれば螢光体スラリー調製時に顔料粒子
をスラリー成分として加えるだけでよく、従つて
従来と全く同じ方法で螢光膜を作成することがで
きる。しかしながら、現在カラーテレビジヨンブ
ラウン管の螢光膜塗布方法として採用されている
回転塗布法では、この螢光体スラリーを用いた場
合、顔料粒子と螢光体粒子の比重、分散性の著し
い相違のために沈降時に螢光体粒子と顔料粒子が
分離し、回転速度や沈降時間の微妙な違いで、螢
光膜に固定される顔料粒子量が変化する。このた
め品質の安定した螢光膜を得ることが困難であ
り、実用には問題がある。 A third method is to prepare a phosphor slurry by dispersing pigment particles together with phosphor particles in a photosensitive aqueous solution, and apply this phosphor slurry onto a face plate in a conventional manner to form a phosphor film. This is the way to do it. According to this method, it is only necessary to add pigment particles as a slurry component when preparing a phosphor slurry, and therefore a phosphor film can be prepared in exactly the same manner as conventional methods. However, in the spin coating method that is currently used as a method for coating phosphor films on color television cathode ray tubes, when this phosphor slurry is used, there is a significant difference in specific gravity and dispersibility between pigment particles and phosphor particles. During sedimentation, the phosphor particles and pigment particles separate, and subtle differences in rotational speed and sedimentation time change the amount of pigment particles fixed on the phosphor film. For this reason, it is difficult to obtain a fluorescent film of stable quality, which poses a problem in practical use.
本発明は上述の第３の方法の欠点である顔料粒
子と螢光体粒子の塗布時における分離の問題を解
決する螢光体スラリーの調製方法を提供すること
を目的とするものである。 An object of the present invention is to provide a method for preparing a phosphor slurry that solves the problem of separation of pigment particles and phosphor particles during coating, which is a disadvantage of the third method described above.
顔料粒子と螢光体粒子とが塗布時に分離しない
ようにするためには、螢光体スラリー中において
顔料粒子と螢光体粒子とを何らかの形で結合させ
る必要がある。本発明者等は顔料粒子と螢光体粒
子とが螢光体スラリー中で均一に結合するような
螢光体スラリーの調製方法を種々検討してきた。
その結果、顔料粒子および螢光体粒子のいずれか
一方あるいはその両方を、解離性の被覆剤であら
かじめ処理して水媒体中で顔料粒子および螢光体
粒子が逆の電荷を有するようにし、この顔料粒子
および螢光体粒子を水媒体に分散させて螢光体ス
ラリーを調製すれば、螢光体スラリー中で螢光体
粒子表面に顔料粒子が均一に吸着し、従つてこの
螢光体スラリーを用いて螢光膜を作成する場合に
は、上述のような塗布時における顔料粒子と螢光
体粒子の分離が起こらず、品質の安定した高コン
トラスト螢光膜を得ることができることを見出し
本発明を完成するに至つた。 In order to prevent the pigment particles and phosphor particles from separating during coating, it is necessary to bond the pigment particles and phosphor particles in some way in the phosphor slurry. The present inventors have studied various methods for preparing a phosphor slurry in which pigment particles and phosphor particles are uniformly combined in the phosphor slurry.
As a result, the pigment particles and/or phosphor particles are pretreated with a dissociable coating so that they have opposite charges in the aqueous medium; If a phosphor slurry is prepared by dispersing pigment particles and phosphor particles in an aqueous medium, the pigment particles will be uniformly adsorbed to the surface of the phosphor particles in the phosphor slurry. This paper found that when a fluorescent film is created using a phosphor film, separation of pigment particles and phosphor particles does not occur during coating as described above, and a high-contrast phosphor film with stable quality can be obtained. The invention was completed.
すなわち、本発明の螢光体スラリーの調製方法
は、顔料粒子および螢光体粒子のいずれか一方あ
るいはその両方を、解離性の被覆剤であらかじめ
処理して水媒体中で顔料粒子および螢光体粒子が
逆の電荷を有するようにし、この顔料粒子および
螢光体粒子を水媒体中に分散させて螢光体スラリ
ーとし、この螢光体スラリー中で螢光体粒子表面
に顔料粒子を吸着させることを特徴とする。 That is, the method for preparing a phosphor slurry of the present invention involves pre-treating either or both of pigment particles and phosphor particles with a dissociable coating agent, and then preparing the pigment particles and phosphor particles in an aqueous medium. The particles have opposite charges, the pigment particles and the phosphor particles are dispersed in an aqueous medium to form a phosphor slurry, and the pigment particles are adsorbed onto the surface of the phosphor particles in the phosphor slurry. It is characterized by
本発明は、従来一般に行なわれている光印刷法
によつて螢光膜を作成する場合に用いられる、ポ
リビニルコルコール、重クロム酸アンモニウム等
を水に溶解した感光性水溶液に顔料粒子および螢
光体粒子を分散してなる螢光体スラリーに主とし
て適用されるものであるが、これに限られるもの
ではなく、例えば沈降塗布法によつて螢光膜を作
成する場合等に用いられる、水あるいは水に適当
な物質を溶解した水溶液に顔料粒子および螢光体
粒子を分散してなる螢光体スラリーにも適用する
ことができる。従つて、本明細書において「水媒
体」とは、感光性水溶液も含めた水溶液および水
を意味するものである。 In the present invention, pigment particles are added to a photosensitive aqueous solution prepared by dissolving polyvinylcolcol, ammonium dichromate, etc. in water, which is used when creating a fluorescent film by the conventionally commonly used photoprinting method. It is mainly applied to fluorescent slurry made by dispersing body particles, but is not limited to this. For example, water or It can also be applied to a phosphor slurry made by dispersing pigment particles and phosphor particles in an aqueous solution in which a suitable substance is dissolved in water. Therefore, in this specification, the term "aqueous medium" means an aqueous solution including a photosensitive aqueous solution and water.
本発明の方法においては先ず、顔料粒子および
螢光体粒子のいずれか一方あるいはその両方を、
解離性の有機あるいは無機の被覆剤で処理して水
媒体中で顔料粒子と螢光体粒子が逆の電荷を有す
るようにする。次にこの顔料粒子および螢光体粒
子を感光体水溶液等の水媒体中に投入し充分撹拌
して水媒体中に顔料粒子および螢光体粒子を分散
させると、顔料粒子は螢光体粒子表面に吸着され
て固定される。なお被覆剤処理によつて顔料粒子
および螢光体粒子の少なくとも一方の表面状態が
両性になつている場合には、水媒体のPH値を顔料
粒子と螢光体粒子の電荷が逆になるような領域に
調整する。 In the method of the present invention, first, one or both of pigment particles and phosphor particles are
Treatment with a dissociable organic or inorganic coating causes the pigment particles and phosphor particles to have opposite charges in the aqueous medium. Next, the pigment particles and phosphor particles are poured into an aqueous medium such as a photoreceptor aqueous solution and sufficiently stirred to disperse the pigment particles and phosphor particles in the aqueous medium. It is adsorbed and fixed. If the surface state of at least one of the pigment particles and phosphor particles becomes amphoteric due to coating treatment, the pH value of the aqueous medium should be adjusted so that the charges of the pigment particles and phosphor particles are opposite. Adjust to the correct area.
本発明の方法に用いられる有機あるいは無機の
被覆剤としては水媒体中での解離性が強いものが
望ましい。水媒体中で解離してマイナスの電荷を
帯びる被覆剤としては、アクリル酸、メタアクリ
ル酸、イタコン酸、フマル酸、無水マレイン酸等
の遊離もしくは無水物形のカルボキシル基を有す
る不飽和モノマーの重合体もしくはそれらを用い
た共重合体が挙げられる。また水媒体中で解離し
てプラスの電荷を帯びる被覆剤としては、ビニル
ピリジン、アクリルモルホリン、アクリル酸ジメ
チルアミノエチル、メタクリル酸ジメチルアミノ
エチル、エチレンイミノ等の一級、二級、三級ア
ミノ基を有するモノマーから得られる重合体もし
くはそれらを用いた共重合体が挙げられる。さら
に両性の被覆剤としては、有機物では遊離カルボ
キシル基と一級、二級、三級アミノ基の両方を有
する重合体や天然物が挙げられ、ゼラチンはその
一例であり、無機物では二酸化珪素等の酸化物が
挙げられる。 The organic or inorganic coating used in the method of the present invention is preferably one that has strong dissociation properties in an aqueous medium. Coating agents that dissociate in an aqueous medium and become negatively charged include heavy unsaturated monomers having free or anhydrous carboxyl groups such as acrylic acid, methacrylic acid, itaconic acid, fumaric acid, and maleic anhydride. Examples include combinations or copolymers using them. Coating agents that dissociate in an aqueous medium and become positively charged include primary, secondary, and tertiary amino groups such as vinylpyridine, acrylic morpholine, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, and ethyleneimino. Examples include polymers obtained from monomers having the same or copolymers using them. Furthermore, as amphoteric coating agents, organic materials include polymers and natural products that have both free carboxyl groups and primary, secondary, and tertiary amino groups, gelatin is one example, and inorganic materials include oxidized materials such as silicon dioxide. Things can be mentioned.
本発明の方法に用いられる螢光体および顔料
は、水溶性あるいは水中で不安定なものでなけれ
ばいかなるものであつてもよい。特にカラーテレ
ビジヨンブラウン管の高コントラスト螢光膜を作
成するのに用いられる螢光体としては、赤色発光
螢光体としてY2O2S：Eu螢光体、Y2O3：Eu螢光
体、YVO4：Eu螢光体等、緑色発光螢光体として
ZnS：Cu、Al螢光体、（Zn、Cd）Ｓ：Cu、Al螢
光体、ZnS：Cu、Au、Al螢光体等、また青色発
光螢光体としてZnS：Ag螢光体、ZnS：Ag、Al
螢光体等が挙げられる。同じくカラーテレビジヨ
ンブラウン管の高コントラスト螢光膜を作成する
のに用いられる顔料としては、赤色顔料としてべ
んがら、硫セレン化カドミウム、鉛丹等、緑色顔
料として酸化クロム等、また青色顔料としてアル
ミン酸コバルト、群青等が挙げられる。 The phosphors and pigments used in the method of the present invention may be of any type as long as they are water-soluble or unstable in water. In particular , phosphors used to create high-contrast phosphor films for color television cathode ray tubes include Y2O2S :Eu phosphor and Y2O3 :Eu phosphor as red-emitting phosphors. , YVO 4 : Eu phosphor, etc., as a green-emitting phosphor
ZnS: Cu, Al phosphor, (Zn, Cd)S: Cu, Al phosphor, ZnS: Cu, Au, Al phosphor, etc. Also, as a blue-emitting phosphor, ZnS: Ag phosphor, ZnS :Ag, Al
Examples include fluorescent materials. Pigments used to create high contrast fluorescent films for color television cathode ray tubes include red pigments such as red pepper, cadmium selenide, and red lead, green pigments such as chromium oxide, and blue pigments such as cobalt aluminate. , ultramarine, etc.
本発明の方法で調製した螢光体スラリーを用い
て回転塗布法によりフエースプレート上に螢光膜
を作成すると、得られる螢光膜中で顔料粒子は、
投入された螢光体粒子と顔料粒子の比率で均一に
固定される。このことは螢光膜の電子顕微鏡観察
および螢光膜の反射率測定等から確められる。 When a fluorescent film is created on a face plate by a spin coating method using the fluorescent slurry prepared by the method of the present invention, the pigment particles in the resulting fluorescent film are
The ratio of the phosphor particles and pigment particles introduced is fixed uniformly. This can be confirmed by observing the fluorescent film with an electron microscope and measuring the reflectance of the fluorescent film.
本発明によれば、顔料粒子が螢光体粒子中に均
一に分散しており、また品質の安定した高コント
ラスト螢光膜を低コストで作成することができ
る。 According to the present invention, pigment particles are uniformly dispersed in phosphor particles, and a high-contrast phosphor film with stable quality can be produced at low cost.
次に実施例によつて本発明を具体的に説明す
る。 Next, the present invention will be specifically explained with reference to Examples.
実施例 １
平均粒子径が約0.3μであるアルミン酸コバル
ト青色顔料粒子10ｇを90c.c.の水中に懸濁させ、こ
れにカリ水ガラスを二酸化珪素（SiO2）量が0.5ｇ
となるように加えた。さらにこれに充分に撹拌し
ながら酢酸バリウム2.0ｇを加えて、アルミン酸
コバルト青色顔料粒子表面にSiO2をコートし
た。次にこの顔料粒子懸濁液20ｇを、ポリビニー
ルアルコール10ｇ、水250ｇおよび重クロム酸ア
ンモニウム１ｇからなる感光性水溶液に平均粒子
径が約９μの銀付活硫化亜鉛青色発光螢光体粒子
（ZnS：Ag）100ｇを分散せしめた螢光体スラリ
ーに加えて、撹拌しながら酢酸でPH値を５に調整
した。このようにして調製した螢光体スラリー中
においては、アルミン酸コバルト青色顔料粒子は
プラスの電荷を有し、一方ZnS：Ag螢光体粒子
はマイナスの電荷を有し、これによつてZnS：
Ag螢光体粒子表面にアルミン酸コバルト粒子が
吸着している。Example 1 10 g of cobalt aluminate blue pigment particles with an average particle size of about 0.3 μ are suspended in 90 c.c. of water, and potassium water glass is added to this with an amount of silicon dioxide (SiO 2 ) of 0.5 g.
I added it so that Furthermore, 2.0 g of barium acetate was added to this with sufficient stirring to coat the surface of the cobalt aluminate blue pigment particles with SiO 2 . Next, 20 g of this pigment particle suspension was added to a photosensitive aqueous solution consisting of 10 g of polyvinyl alcohol, 250 g of water, and 1 g of ammonium dichromate. :Ag) was added to the dispersed phosphor slurry, and the pH value was adjusted to 5 with acetic acid while stirring. In the phosphor slurry thus prepared, the cobalt aluminate blue pigment particles have a positive charge, while the ZnS:Ag phosphor particles have a negative charge, thereby causing the ZnS:
Cobalt aluminate particles are adsorbed on the surface of Ag phosphor particles.
上述のようにして得た螢光体スラリーを用い
て、回転塗布法でフエースプレート上に螢光膜を
作成した。得られた螢光膜中で顔料粒子は、投入
された螢光体粒子と顔料粒子の比率で均一に分散
され、固定されていることが電子顕微鏡観察およ
び反射率測定から確かめられた。 Using the phosphor slurry obtained as described above, a phosphor film was formed on a face plate by a spin coating method. It was confirmed by electron microscopic observation and reflectance measurement that the pigment particles were uniformly dispersed and fixed in the resulting phosphor film at a ratio of the phosphor particles added to the pigment particles.
実施例 ２
40℃の水100c.c.にゼラチン１ｇを溶解し、これ
に平均粒子径が約９μのZnS：Ag螢光体粒子100
ｇを投入後冷却し、過乾燥してZnS：Ag螢光
体粒子上にゼラチンの薄膜を形成した。この
ZnS：Ag螢光体粒子100ｇと平均粒子径が約0.3μ
であるアルミン酸コバルト青色顔料粒子２ｇと
を、ポリビニルアルコール10ｇ、水250ｇおよび
重クロム酸アンモニウム１ｇからなる感光性溶液
中に投入し、撹拌しながらPH値を6.2に調整し
た。このようにして調製した螢光体スラリー中に
おいては、ZnS：Ag螢光体粒子はプラスの電荷
を有し、一方アルミン酸コバルト青色顔料粒子は
マイナスの電荷を有し、これによつてZnS：Ag
螢光体粒子表面にアルミン酸コバルト粒子が吸着
している。Example 2 1 g of gelatin was dissolved in 100 c.c. of water at 40°C, and 100 ZnS:Ag phosphor particles with an average particle size of about 9 μm were added thereto.
g was added, the mixture was cooled and overdried to form a thin film of gelatin on the ZnS:Ag phosphor particles. this
ZnS: Ag phosphor particles 100g and average particle diameter approximately 0.3μ
2 g of cobalt aluminate blue pigment particles were put into a photosensitive solution consisting of 10 g of polyvinyl alcohol, 250 g of water, and 1 g of ammonium dichromate, and the pH value was adjusted to 6.2 while stirring. In the phosphor slurry thus prepared, the ZnS:Ag phosphor particles have a positive charge, while the cobalt aluminate blue pigment particles have a negative charge, thereby causing the ZnS: Ag
Cobalt aluminate particles are adsorbed on the surface of the phosphor particles.
上述のようにして得た螢光体スラリーを用い
て、回転塗布法でフエースプレート上に螢光膜を
作成した。得られた螢光膜中で顔料粒子は、投入
された螢光体粒子と顔料粒子の比率で均一に分散
され、固定されていることが電子顕微鏡観察およ
び反射率測定から確かめられた。 Using the phosphor slurry obtained as described above, a phosphor film was formed on a face plate by a spin coating method. It was confirmed by electron microscopy observation and reflectance measurement that the pigment particles were uniformly dispersed and fixed in the resulting phosphor film at a ratio of phosphor particles to pigment particles.
実施例 ３
40℃の水100c.c.にゼラチン１ｇを溶解し、これ
に平均粒子径が約６μのユーロピウム付活酸硫化
イツトリウム螢光体粒子（Y2O2S：Eu）100ｇを
投入後冷却し、ホルマリンでゼラチンを硬化して
過乾燥し、Y2O2S：Eu螢光体粒子上にゼラチ
ンの薄膜を形成した。Example 3 After dissolving 1 g of gelatin in 100 c.c. of water at 40°C and adding 100 g of europium-activated yttrium oxysulfide phosphor particles (Y 2 O 2 S: Eu) with an average particle size of about 6 μm, After cooling, the gelatin was hardened with formalin and overdried to form a thin film of gelatin on the Y2O2S :Eu phosphor particles.
一方平均粒子径が約0.3μのべんがら赤色顔料
粒子10ｇを90c.c.の水中に懸濁させ、これにアニオ
ン性のアクリル酸エチルのエマルジヨン（エチル
アクリレート／メチルメタクリレート＝７／３）
をアクリル酸エチルとして0.5ｇ投入し、酢酸で
PH値を４にして過乾燥した。得られたものを90
c.c.の水中でボールミル粉砕し、顔料粒子分散液と
した。 On the other hand, 10g of red pigment particles with an average particle diameter of about 0.3μ are suspended in 90cc of water, and anionic ethyl acrylate emulsion (ethyl acrylate/methyl methacrylate = 7/3) is added to this.
Add 0.5g of ethyl acrylate and add acetic acid.
The pH value was set to 4 and the mixture was overdried. 90 what you got
The mixture was ground in a ball mill in cc of water to obtain a pigment particle dispersion.
次に上記ゼラチン処理Y2O2S：Eu螢光体粒子
100ｇと上記顔料粒子分散液３ｇとを、ポリビニ
ルアルコール10ｇ、水250ｇおよび重クロム酸ア
ンモニウム１ｇとからなる感光性溶液中に投入
し、撹拌しながらPH値を6.5に調整した。このよ
うにして調製した螢光体スラリー中においては、
Y2O2S：Eu螢光体粒子はプラスの電荷を有し、
一方べんがら赤色顔料粒子はマイナスの電荷を有
し、これによつてY2O2S：Eu螢光体粒子表面に
べんがら粒子が吸着している。 Next, the above gelatin-treated Y 2 O 2 S:Eu phosphor particles
100 g of the above pigment particle dispersion were put into a photosensitive solution consisting of 10 g of polyvinyl alcohol, 250 g of water, and 1 g of ammonium dichromate, and the pH value was adjusted to 6.5 while stirring. In the phosphor slurry prepared in this way,
Y 2 O 2 S: Eu phosphor particles have a positive charge,
On the other hand, the red pigment particles have a negative charge, which causes them to be adsorbed on the surface of the Y 2 O 2 S:Eu phosphor particles.
上述のようにして得た螢光体スラリーを用い
て、回転塗布法でフエースプレート上に螢光膜を
作成した。得られた螢光膜中で顔料粒子は、投入
された螢光体粒子と顔料粒子の比率で均一に分散
され、固定されていることが電子顕微鏡観察およ
び反射率測定から確かめられた。 Using the phosphor slurry obtained as described above, a phosphor film was formed on a face plate by a spin coating method. It was confirmed by electron microscopic observation and reflectance measurement that the pigment particles were uniformly dispersed and fixed in the resulting phosphor film at a ratio of the phosphor particles added to the pigment particles.
Claims (1)
るいはその両方を、解離性の被覆剤であらかじめ
処理して水媒体中で顔料粒子および螢光体粒子が
逆の電荷を有するようにし、この顔料粒子および
螢光体粒子を水媒体中に分散させて螢光体スラリ
ーとし、この螢光体スラリー中で螢光体粒子表面
に顔料粒子を吸着させることを特徴とする螢光体
スラリーの調製方法。1 The pigment particles and/or the phosphor particles are pretreated with a dissociable coating agent so that the pigment particles and the phosphor particles have opposite charges in an aqueous medium, and the pigment particles are and a method for preparing a phosphor slurry, which comprises dispersing phosphor particles in an aqueous medium to obtain a phosphor slurry, and adsorbing pigment particles onto the surface of the phosphor particles in the phosphor slurry.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5082378A JPS54143442A (en) | 1978-04-29 | 1978-04-29 | Preparation of slurry of fluorescent material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5082378A JPS54143442A (en) | 1978-04-29 | 1978-04-29 | Preparation of slurry of fluorescent material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS54143442A JPS54143442A (en) | 1979-11-08 |
| JPS6154076B2 true JPS6154076B2 (en) | 1986-11-20 |
Family
ID=12869476
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5082378A Granted JPS54143442A (en) | 1978-04-29 | 1978-04-29 | Preparation of slurry of fluorescent material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS54143442A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR930008207B1 (en) * | 1989-12-22 | 1993-08-26 | 삼성전관 주식회사 | Process for production of alkaline earth sulfur phosphor |
| KR100735320B1 (en) | 2005-12-27 | 2007-07-04 | 삼성전기주식회사 | Formation method of phosphor film and fabrication method of light emitting diode package using the same |
| JP5685820B2 (en) * | 2010-03-11 | 2015-03-18 | 株式会社リコー | Polyacryloylmorpholine-coated pigment dispersion, ink, ink cartridge, and inkjet printer |
-
1978
- 1978-04-29 JP JP5082378A patent/JPS54143442A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS54143442A (en) | 1979-11-08 |
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