JPH03231987A - Fluorescent material and production thereof - Google Patents
Fluorescent material and production thereofInfo
- Publication number
- JPH03231987A JPH03231987A JP11647390A JP11647390A JPH03231987A JP H03231987 A JPH03231987 A JP H03231987A JP 11647390 A JP11647390 A JP 11647390A JP 11647390 A JP11647390 A JP 11647390A JP H03231987 A JPH03231987 A JP H03231987A
- Authority
- JP
- Japan
- Prior art keywords
- phosphor
- silicon
- film
- particles
- surface treatment
- 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
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 239000000463 material Substances 0.000 title abstract description 6
- 239000002245 particle Substances 0.000 claims abstract description 55
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000000049 pigment Substances 0.000 claims abstract description 29
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 23
- 239000010703 silicon Substances 0.000 claims abstract description 21
- -1 silicon alkoxide Chemical class 0.000 claims abstract description 19
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- 239000002904 solvent Substances 0.000 claims abstract description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 8
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 108
- 239000012756 surface treatment agent Substances 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 23
- 239000002210 silicon-based material Substances 0.000 claims description 15
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 150000003377 silicon compounds Chemical class 0.000 abstract description 7
- 230000007062 hydrolysis Effects 0.000 abstract description 5
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 5
- 150000004703 alkoxides Chemical class 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 2
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 19
- 229910001853 inorganic hydroxide Inorganic materials 0.000 description 17
- 239000002002 slurry Substances 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000001055 blue pigment Substances 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
- 239000000243 solution Substances 0.000 description 8
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 238000011084 recovery Methods 0.000 description 6
- 238000004381 surface treatment Methods 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 5
- 239000000853 adhesive Substances 0.000 description 5
- 230000001070 adhesive effect Effects 0.000 description 5
- 239000007810 chemical reaction solvent Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 230000008929 regeneration Effects 0.000 description 4
- 238000011069 regeneration method Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 230000003301 hydrolyzing effect Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- JOSWYUNQBRPBDN-UHFFFAOYSA-P ammonium dichromate Chemical compound [NH4+].[NH4+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O JOSWYUNQBRPBDN-UHFFFAOYSA-P 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000012864 cross contamination Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 229940072033 potash Drugs 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 235000015320 potassium carbonate Nutrition 0.000 description 2
- 235000019353 potassium silicate Nutrition 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 2
- QSLPNSWXUQHVLP-UHFFFAOYSA-N $l^{1}-sulfanylmethane Chemical compound [S]C QSLPNSWXUQHVLP-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- RNRZLEZABHZRSX-UHFFFAOYSA-N diiodosilicon Chemical compound I[Si]I RNRZLEZABHZRSX-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000005520 electrodynamics Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- GNBHRKFJIUUOQI-UHFFFAOYSA-N fluorescein Chemical compound O1C(=O)C2=CC=CC=C2C21C1=CC=C(O)C=C1OC1=CC(O)=CC=C21 GNBHRKFJIUUOQI-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Landscapes
- Luminescent Compositions (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明はカラー受像管の螢光膜用等に使用される螢光体
及びその製造方法に関し、更に詳しくは、成膜性に優れ
、かつ、顔料や無機物の表面処理剤等の付着力を向上さ
せた螢光体及びその製造方法に関する。[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a phosphor used for a phosphor film of a color picture tube, etc., and a method for manufacturing the same, and more specifically, it relates to a phosphor that has excellent film formability and , relates to a phosphor with improved adhesion to pigments, inorganic surface treatment agents, etc., and a method for producing the same.
周知のようにカラー受像管の螢光膜を形成する場合、例
えばポリビニルアルコール（ＰＶＡ）と重クロム酸アン
モニウム（ＡＤＣ）と界面活性剤（ＳＡＡ）を含む水溶
液に特定の螢光体を分散させた螢光体スラリーを調製し
、これを受像管のフエースプレート（ガラスパネル）面
に全面塗布した後、シャドウマスクを介して所定のパタ
ーン（ドツト又はストライプ）に紫外線を照射して、照
射された部位を硬化させて水不溶化する（露光工程）。As is well known, when forming a phosphor film for a color picture tube, a specific phosphor is dispersed in an aqueous solution containing, for example, polyvinyl alcohol (PVA), ammonium dichromate (ADC), and a surfactant (SAA). After preparing a phosphor slurry and applying it to the entire surface of the face plate (glass panel) of the picture tube, ultraviolet rays are irradiated in a predetermined pattern (dots or stripes) through a shadow mask, and the irradiated area is is cured to make it water-insoluble (exposure process).
次に非露光部の水溶性の螢光膜を水洗し、除去して所望
のパターンの螢光膜を得る（現像工程）。この工程を３
回繰返して緑色発光螢光膜、青色発光螢光膜及び赤色発
光螢光膜を順次形成する。Next, the water-soluble fluorescent film in the non-exposed area is washed with water and removed to obtain a fluorescent film with a desired pattern (development step). This process 3
This is repeated several times to sequentially form a green-emitting fluorescent film, a blue-emitting fluorescent film, and a red-emitting fluorescent film.
そして、上述のような工程でカラー受像管の螢光膜を形
成する場合、
■螢光膜のフェースプレート（ガラスパネル）面との接
着力が強いこと、
■現像後の螢光膜ストライブ又はドツトが所定の寸法精
度に仕上がり、ピンホールやツブ（凝集粒子）が少ない
こと、
■螢光膜形成工程において１つの発光成分の螢光体が他
の発光成分の螢光膜上又はガラスパネル面上に混入、付
着（クロスコンタミネーション）しないこと
等が要求されるところから、これらの要求を満たし得る
螢光体、即ち、スラリー中での分散性が優れ、成膜性の
良好な螢光体の開発が望まれている。When forming a fluorescent film for a color picture tube using the above-mentioned process, the adhesive force of the fluorescent film to the face plate (glass panel) surface is strong, and the fluorescent film strips or The dots are finished with the specified dimensional accuracy, and there are few pinholes or blobs (agglomerated particles). ■ In the fluorescent film forming process, the phosphor of one luminescent component is placed on the fluorescent film of another luminescent component or on the glass panel surface. Since there is a requirement that there be no contamination or adhesion (cross-contamination) on the surface, we need a phosphor that can meet these requirements, that is, a phosphor that has excellent dispersibility in slurry and good film-forming properties. development is desired.
また、螢光膜形成時、現像工程で水洗、除去された、非
露光部の螢光体は回収して再使用されるが、表面に顔料
粒子を付着させた顔料イ１螢光体や無機物質で表面コー
トされた螢光体を回収再生する場合、表面に付着した顔
料や表面処理剤が−」１記回収工程において剥離するた
め、再使用にあたって再度顔料付けや表面処理を行う必
要があり、コスト的にも不満足であるという問題点があ
った。In addition, during the formation of a fluorescent film, the phosphor in the non-exposed area that is washed with water and removed in the development process is collected and reused. When recovering and recycling a phosphor whose surface has been coated with a substance, the pigments and surface treatment agents that adhere to the surface will peel off during the recovery process, so it is necessary to reapply the pigment and treat the surface before reusing it. However, there was a problem in that it was unsatisfactory in terms of cost.
そこで上記各問題点解決のため、種々改良が試みられて
おり、例えばガラスパネルへの接着力アップとクロスコ
ンタミネーションを防止する目的で螢光体粒子表面にＳ
ｉｎ、とアルミニウム化合物と亜鉛の化合物からなる表
面物質をコートする方法（特公昭６１４６５１２号）、
螢光体の分散性、撥水性を高めるため、螢光体粒子の表
面にシラン膜を形成する方法（特公昭５１−１７５５５
号）、螢光体と顔料の付着力を向上させるため、螢光体
粒子の表面をシリカの連続皮膜で被覆する方法（特公昭
５９−１０７０９号）等をはじめ、珪素系の化合物によ
る表面処理方法が多数提案されている。Therefore, in order to solve the above problems, various improvements have been attempted. For example, in order to increase adhesive strength to glass panels and prevent cross-contamination, S
A method of coating a surface substance consisting of a compound of aluminum and zinc (Japanese Patent Publication No. 6146512),
A method of forming a silane film on the surface of phosphor particles in order to improve the dispersibility and water repellency of the phosphor (Japanese Patent Publication No. 51-17555
In order to improve the adhesion between the phosphor and the pigment, surface treatments using silicon-based compounds, including a method of coating the surface of the phosphor particles with a continuous film of silica (Japanese Patent Publication No. 10709/1983), etc. Many methods have been proposed.
しかしながら、用いられる螢光体の親水度、表面動電位
等のいわゆる表面性状が螢光体の焼成条件や、その後に
実施されるボールミル分散条件等の違いによって変化し
、所定の範囲に管理することが困難なため、従来の表面
処理法によって得られた螢光体は必ずしも成膜性が十分
ではなかった。However, the so-called surface properties such as hydrophilicity and surface electrodynamics of the phosphor used vary depending on the firing conditions of the phosphor and the subsequent ball mill dispersion conditions, and it is difficult to manage them within a predetermined range. Because of the difficulty in surface treatment, phosphors obtained by conventional surface treatment methods did not necessarily have sufficient film formability.
また螢光体と顔料粒子や種々の表面処理剤との接着が未
だ不充分なためにこの螢光体の回収再生時に顔料粒子や
表面処理剤が部分的に剥離し、再使用に際して再び顔料
付けや表面処理を施す必要があったりする場合が多く、
従って、その改良が望まれていた。Furthermore, because the adhesion between the phosphor and the pigment particles and various surface treatment agents is still insufficient, the pigment particles and surface treatment agents are partially peeled off when the phosphor is recovered and recycled, and the pigment particles and surface treatment agents must be reapplied when reused. In many cases, it is necessary to perform surface treatment.
Therefore, improvement thereof has been desired.
本発明は上述のような状況に鑑みてなされたものであり
、螢光体粒子の表面性状を安定化させることによって、
この螢光体を用いて螢光膜を形成する際に、螢光体スラ
リー組成の変化に影響されることなく良好な螢光膜が得
られると共に、従来の螢光体に比べて螢光体と顔料や表
面処理剤との接着力が大である螢光体及びその製造方法
を提供することを目的とする。The present invention was made in view of the above-mentioned situation, and by stabilizing the surface properties of phosphor particles,
When forming a phosphor film using this phosphor, a good phosphor film can be obtained without being affected by changes in the phosphor slurry composition. The object of the present invention is to provide a phosphor that has a high adhesive strength with pigments and surface treatment agents, and a method for producing the same.
そこで本発明者等は上記目的達成のため螢光体の表面処
理方法について鋭意研究の結果、螢光体の表面に顔料や
無機物の表面処理剤を付着させる前もしくはこれらを付
着させた後にこの螢光体粒子を懸濁させた溶媒中で珪素
のアルコキサイドもしくはその誘導体を加水分解させる
ことによって得られた、少なくとも一部が珪素原子に結
合した水酸基を含有する珪素化合物の皮膜を螢光体粒子
表面に所定量付着させる処理を施して、該螢光体のメタ
ノールウェツタビリテイ−（ＭＷ値）が所定の値を示す
ように調整することにより上記目的が達成され得ること
を見出し、本発明に至った。Therefore, in order to achieve the above object, the present inventors conducted intensive research on surface treatment methods for phosphors, and found that the phosphors were coated with pigments or inorganic surface treatment agents before or after attaching them to the surface of the phosphor. The surface of the phosphor particles is coated with a film of a silicon compound containing hydroxyl groups, at least a portion of which is bonded to silicon atoms, obtained by hydrolyzing a silicon alkoxide or its derivative in a solvent in which the phosphor particles are suspended. It has been discovered that the above object can be achieved by subjecting the phosphor to a predetermined amount of adhesion and adjusting the methanol wettability (MW value) of the phosphor to a predetermined value. It's arrived.
即ち、本発明の螢光体は珪素の量に換算して０゜１〜２
５ｍｇ／ｍ”の、少なくとも一部が珪素原子に結合しま
た水酸基を含有する珪素系化合物の皮膜と、顔料粒子お
よび／又は前記珪素系化合物以外の無機物の表面処理剤
とが表面に付着しており、メタノールウェツタビリテイ
−（ＭＷ値）が０〜２０％であることを特徴とする。That is, the phosphor of the present invention has a silicon content of 0°1 to 2
5mg/m'' of a film of a silicon-based compound at least partially bonded to silicon atoms and containing hydroxyl groups, and a pigment particle and/or an inorganic surface treatment agent other than the silicon-based compound attached to the surface. It is characterized by a methanol wettability (MW value) of 0 to 20%.
更に、本発明の螢光体の製造方法は表面に顔料粒子およ
び／又は無機物の表面処理剤を付着させる前の螢光体も
しくはこれらを付着させた螢光体と、珪素のアルコキサ
イドまたはその誘導体とを含む溶媒中に触媒を添加して
上記珪素のアルコキサイド又はその誘導体を加水分解し
た後、重縮合させ、次いで溶媒を除去することを特徴と
する。Furthermore, the method for producing a phosphor of the present invention involves the use of a phosphor before or with pigment particles and/or an inorganic surface treatment agent attached thereto, and a silicon alkoxide or a derivative thereof. The method is characterized in that a catalyst is added to a solvent containing the above to hydrolyze the silicon alkoxide or its derivative, followed by polycondensation, and then the solvent is removed.
以下、本発明を更に詳細に説明する。The present invention will be explained in more detail below.
本発明で使用されるシリコンアルコキサイＦは一般式Ｓ
ｉ （ＯＲ） ４ （Ｒ：アルキル基）で表わさ
れ、通常アルキル基の炭素数は１〜５程度であるが、反
応性や工業規模での入手の容易さなどから炭素数１〜３
すなわち、テトラメトキシシラン、テトラメトキシシラ
ン、テトラプロポキシシランなどが好適に用いられる。The silicon alkoxy F used in the present invention has the general formula S
i (OR) 4 (R: alkyl group), and the number of carbon atoms in the alkyl group is usually about 1 to 5, but the number of carbon atoms is 1 to 3 due to reactivity and ease of availability on an industrial scale.
That is, tetramethoxysilane, tetramethoxysilane, tetrapropoxysilane, etc. are preferably used.
また、シリコンアルコキサイドの誘導体、例えば上記シ
リコンアルコキサイドを部分的に加水分解して得られる
低縮合物誘導体を用いても良い。Further, derivatives of silicon alkoxide, such as low condensate derivatives obtained by partially hydrolyzing the silicon alkoxide described above, may also be used.
更にこれらＳｉアルコキサイド又はその誘導体と共に一
般式Ｍ２０・ｘｓｉｃｈ（但し、Ｍはり、１゜Ｎａ、に
およびＮＨ，の中の少なくとも１種であり、Ｘはその化
合物中のＳｉＯ，７Ｍ２０のモル比）で表わされる珪酸
塩化合物を併用しても良い。Furthermore, together with these Si alkoxides or derivatives thereof, compounds with the general formula M20 x sich (where M is at least one of 1° Na, NH, and X is the molar ratio of SiO, 7M20 in the compound) are used. The silicate compounds shown may also be used in combination.
次に、本発明で使用される触媒としては、アンモニア、
アンモニウム塩、ＮａＯＨ，ＫＯＨ，ＬｉＯＨなどの塩
基性触媒や、Ｈａｓ ０４． ＨＣｅなどの酸性触媒が
使用可能であるが、反応処理後の触媒除去の容易さなど
から塩基性触媒が好ましく、特にアンモニアが好適に用
いられる。Next, the catalyst used in the present invention includes ammonia,
Basic catalysts such as ammonium salts, NaOH, KOH, LiOH, Has 04. Although acidic catalysts such as HCe can be used, basic catalysts are preferred from the viewpoint of ease of catalyst removal after reaction treatment, and ammonia is particularly preferred.
さらに、本発明で使用される反応溶媒としては、シリコ
ンアルコキサイド、上記の触媒および加水分解の原料と
して加えられる水を溶解し、かつ、螢光体粒子を良く分
散させるものであれば特に限定されないが、例えば、メ
タノール、エタノール、イソプロパツールなどの種々の
アルコールが好適に用いられる。また、本発明において
は、粒子の凝集を防止する目的でアルコールに炭化水素
を混合してもよい。この炭化水素はアルコールと相溶性
があるものであれば特に限定されないが、溶媒回収の容
易さなどから炭素数５〜１２の脂肪族、脂環族、芳香族
炭化水素、より好ましくは、炭素数６〜９の炭化水素が
良い。例えば、ｎ−ヘキサン、ｎ−ヘプタン、シクロヘ
キサン、メチル−シクロヘキサン、ベンゼン、トルエン
、キシレン、アセトンなどである。Furthermore, the reaction solvent used in the present invention is particularly limited as long as it dissolves the silicon alkoxide, the above-mentioned catalyst, and water added as a raw material for hydrolysis, and disperses the phosphor particles well. However, various alcohols such as methanol, ethanol, and isopropanol are preferably used. Further, in the present invention, a hydrocarbon may be mixed with alcohol for the purpose of preventing particle agglomeration. This hydrocarbon is not particularly limited as long as it is compatible with alcohol, but from the viewpoint of ease of solvent recovery, aliphatic, alicyclic, and aromatic hydrocarbons having 5 to 12 carbon atoms, more preferably carbon atoms. 6 to 9 hydrocarbons are preferred. Examples include n-hexane, n-heptane, cyclohexane, methyl-cyclohexane, benzene, toluene, xylene, and acetone.
まず、本発明では、反応溶媒に水および触媒をそれぞれ
溶解し、これに螢光体粒子を分散させ、次いでシリコン
アルコキサイド又はその誘導体を添加して加水分解・重
縮合反応を行なわせる。反応溶液中に加える螢光体粒子
添加量は、撹拌状態で粒子の分散状態が維持されるかぎ
り特に限定されないが、通常は反応溶液１１に対し、５
００〜１０００ｇの範囲から選ばれる。First, in the present invention, water and a catalyst are each dissolved in a reaction solvent, phosphor particles are dispersed therein, and then silicon alkoxide or a derivative thereof is added to carry out a hydrolysis/polycondensation reaction. The amount of phosphor particles added to the reaction solution is not particularly limited as long as the dispersed state of the particles is maintained in the stirring state, but usually 5 to 11 parts of the reaction solution is added.
It is selected from the range of 00 to 1000 g.
シリコンアルコキサイド又はその誘導体の加水分解・重
縮合反応を行わせ、その生成物からなる皮膜を螢光体粒
子表面に付着させるための条件は螢光体粒子の大きさな
どにより異なるため、−概には決定できないが、例えば
反応溶媒系中の水の濃度は０．５〜５０ｎ＋ｏＩ！、／
ｆｆ、触媒の濃度は０．１〜１０ｍｏｊ２／／２、Ｓｉ
アルコキサイド又はその誘導体の濃度は通常０．０１〜
０．１ ｍｏｆ ／ ｐ、の範囲から選ばれる。The conditions for carrying out the hydrolysis/polycondensation reaction of silicon alkoxide or its derivatives and attaching the film made of the product to the surface of the phosphor particles vary depending on the size of the phosphor particles, etc. Although it cannot be determined generally, for example, the concentration of water in the reaction solvent system is between 0.5 and 50n+oI! ,/
ff, catalyst concentration 0.1-10moj2//2, Si
The concentration of alkoxide or its derivative is usually 0.01~
0.1 mof/p, selected from the range.
また、反応溶媒、水、触媒および螢光体粒子からなる系
に対しシリコンアルコキサイドを添加する方法は、−度
に全量を添加してもよいし、滴下などにより分割添加し
てもよい。反応は、撹拌下で、通常ば０〜５０°Ｃの温
度範囲で行なわれるが、反応時間を短縮するなどの目的
で、還流条件下でさらに高温で反応させてもよい。Furthermore, the silicon alkoxide may be added to the system consisting of the reaction solvent, water, catalyst and phosphor particles by adding the entire amount at one time or by adding it in portions by dropwise addition or the like. The reaction is usually carried out under stirring at a temperature in the range of 0 to 50°C, but for the purpose of shortening the reaction time, the reaction may be carried out at a higher temperature under reflux conditions.
次に、反応終了後の粒子は、沈降分離または濾過などの
方法により反応溶液から分離した後、乾燥される。Next, the particles after the reaction is separated from the reaction solution by a method such as sedimentation or filtration, and then dried.
このようにして得られた螢光体粒子表面の一部分もしく
は全面には反応溶媒中に添加されたシリコンアルコキサ
イド又はその誘導体の加水分解・０
重縮合によって生成した珪素系化合物の皮膜が形成され
る。この珪素系化合物は、通常、−３ｉＯ−の繰返し結
合鎖を有し、珪素原子には水酸基と一部にアルコキシ基
が結合しているが、それらの基のほか、シリコンアルコ
キサイドの不純物もしくは何らかの目的で添加された、
他の珪素化合物に由来するアルカリ金属、水素原子、ハ
ロゲン、アルキル基等を含有していても良い。A film of a silicon-based compound produced by hydrolysis and polycondensation of silicon alkoxide or its derivatives added to the reaction solvent is formed on a part or the entire surface of the phosphor particles thus obtained. Ru. This silicon-based compound usually has a -3iO- repeating bond chain, and the silicon atom has a hydroxyl group and some alkoxy groups bonded to it, but in addition to these groups, impurities of silicon alkoxide or added for some purpose
It may contain alkali metals, hydrogen atoms, halogens, alkyl groups, etc. derived from other silicon compounds.
かかる珪素系化合物は本発明の目的を充足する限りその
他の珪素化合物、例えば一般弐Ｍ ２０・ｘｓｉＯｚ
（但し、ＭおよびＸは前記と同様である）で表わされ
る珪酸塩化合物を含んでいても良い。（以下、これらの
珪素系化合物を総称して、［Ｓｉの無機水酸化物」とい
うことにする）。本発明では簡便にはシリコンアルコキ
サイドの加水分解によりかかるＳｉの無機水酸化物から
成る連続皮膜を、凝集させずして均一に付着させること
が可能となる。その結果、螢光体表面性状が安定化する
ため、この螢光体を用いて螢光膜とした時の螢光膜特性
の再現性が良好となる。Such silicon-based compounds may include other silicon compounds, such as general 2M 20.
(However, M and X are the same as above.) It may contain the silicate compound represented by. (Hereinafter, these silicon-based compounds will be collectively referred to as "inorganic hydroxide of Si"). In the present invention, a continuous film made of an inorganic hydroxide of Si can be simply and uniformly deposited by hydrolyzing silicon alkoxide without causing agglomeration. As a result, the surface properties of the phosphor are stabilized, so that when this phosphor is used to form a fluorescent film, the reproducibility of the fluorescent film properties is improved.
１
ところで、水濡れ性の良好な螢光体はどスラリー中での
分散性が良く、しかも顔料等との接着力は強いが、得ら
れる螢光体の水濡れ性は簡易的には例えば特開昭６１−
２３９８７号公報に記載されているＭＷ値（メタノール
ウェツタビリテイ法、即ち、粒子が完全に濡れるメタノ
ールの容量％の値）で評価が可能である。1 Incidentally, a phosphor with good water wettability has good dispersibility in a slurry and has strong adhesion to pigments, etc., but the water wettability of the obtained phosphor can be summarized simply as, for example, 1986-
Evaluation can be made using the MW value (methanol wettability method, that is, the value of volume % of methanol that completely wets the particles) described in Japanese Patent No. 23987.
そして、本発明の螢光体においては得られる螢光体の水
濡れ性の点でこの螢光体のＭＷ値が０〜２０％の範囲の
ものが好ましく、特に０〜１０％の範囲にあるものがよ
り好ましい。そのために、用いられる螢光体の表面性状
に応じて表面処理に使用される原料としてのＳｉアルコ
キサイド又はその誘導体の量がコントロールされるが、
最終的に螢光体表面に付着したＳｉの無機水酸化物から
なる皮膜の重量が、Ｓｉの重量に換算しておよそＱ、１
ｍｇ／ｍ２より少ない場合はＳｉの無機水酸化物からな
る皮膜を設けない、もとの螢光体の表面性状に左右され
るため、その成膜性に再現性がなく、また顔料や無機物
の表面処理剤との接着力が十分２
ではない。また、逆にＳｉの無機水酸化物からなる皮膜
の量を２５ｍｇ／ｍ２よりも多くすると得られる螢光体
の発光輝度の経時的な低下が著しく、しかもこれを加熱
、乾燥処理した時、螢光体粒子同士が接着、凝集し、成
膜性が極めて悪くなる。従って本発明によって得られた
螢光体の粒子表面に付着させる、Ｓｉの無機水酸化物か
らなる皮膜の付着量はＳｉの重量に換算しておよそ０．
１〜２５１Ｉ１ｇ／ｌｌ１２とするのが好ましく、特に
およそ１〜８ｍｇ／ｌ１１２とするのがより好ましい。In the phosphor of the present invention, from the viewpoint of water wettability of the obtained phosphor, it is preferable that the MW value of the phosphor is in the range of 0 to 20%, particularly in the range of 0 to 10%. is more preferable. For this purpose, the amount of Si alkoxide or its derivatives used as a raw material for surface treatment is controlled depending on the surface properties of the phosphor used.
The weight of the film made of inorganic Si hydroxide that finally adheres to the surface of the phosphor is approximately Q, 1 in terms of the weight of Si.
If the amount is less than mg/m2, a film made of inorganic Si hydroxide will not be applied; it will depend on the surface properties of the original phosphor, and the film formation will not be reproducible. The adhesive strength with the surface treatment agent is not sufficient. Conversely, when the amount of the film made of inorganic hydroxide of Si is increased to more than 25 mg/m2, the luminance of the resulting phosphor decreases markedly over time. The light particles adhere to each other and aggregate, resulting in extremely poor film-forming properties. Therefore, the amount of the film made of an inorganic Si hydroxide deposited on the particle surface of the phosphor obtained by the present invention is approximately 0.00% in terms of the weight of Si.
Preferably, it is between 1 and 251 I1g/112, more preferably between about 1 and 8 mg/112.
次いで、上述のようにして得た螢光体の表面に従来公知
の方法により、出来るだけその螢光体の発光光は透過し
てそれ以外の光も吸収し得る顔料粒子および／又はＡ２
□Ｃｈ、Ｔｉ０ｚ等の、Ｓｉの無機水酸化物以外の無機
物の表面処理剤を付着させて、本発明の螢光体を得る。Next, pigment particles and/or A2 that can transmit as much of the light emitted from the phosphor as possible and absorb other light are applied to the surface of the phosphor obtained as described above by a conventionally known method.
□A phosphor of the present invention is obtained by attaching an inorganic surface treatment agent other than the inorganic hydroxide of Si, such as Ch or Ti0z.
なお、本発明の螢光体の製造に際してはＳｉの無機水酸
化物を付着させる順序は上記の順序とは逆に、予じめ顔
料および／又は無機物の表面処理剤を表面に付着させた
螢光体を用い、これに上記と同様にしてＳｉＩ２
の無機水酸化物を付着させても良い。In the production of the phosphor of the present invention, the order in which the inorganic hydroxide of Si is attached is opposite to the above order, and the order in which the inorganic hydroxide of Si is attached is reversed. An inorganic hydroxide of SiI2 may be attached to a light body in the same manner as described above.
また、本発明によってＳｔの無機水酸化物から成る皮膜
を付着させる螢光体は、種々の用途のものを選択できる
が、好適例としてはカラーブラウン管用螢光体を挙げる
ことができ、より具体的にはＺｎＳ：Ａｇ、Ｃｆｌ、Ｚ
ｎＳ：Ｃｕ、Ａｊ２、Ｚｎｓ：ｃｕ、Ａｕ、Ａ４２等の
、硫化物を母体とする螢光体を用いた場合、特に良好な
結果が得られる。Further, the phosphor to which the film made of inorganic hydroxide of St is attached according to the present invention can be selected from those for various uses, but a preferable example is a phosphor for a color cathode ray tube; Specifically, ZnS:Ag, Cfl, Z
Particularly good results are obtained when using sulfide-based phosphors such as nS:Cu, Aj2, Zns:cu, Au, A42, etc.
上述のようにして特定量のＳｉの無機水酸化物から成る
皮膜を表面に付着させ、ＭＷ値が所定の値を示すように
調整された本発明の螢光体は成膜性が良好であり、しか
もこの螢光体に付着させた顔料やＡ／２ｚＯ，、Ｔｉ
Ｏｚ等の無機物の表面処理剤の接着力が著しく向上する
ため、螢光膜作成後に螢光体スラリーを回収し、再使用
する場合も顔料や表面処理剤の剥離が少ない。The phosphor of the present invention, in which a film made of a specific amount of inorganic hydroxide of Si is adhered to the surface as described above and whose MW value is adjusted to a predetermined value, has good film formability. , Moreover, the pigment attached to this phosphor and A/2zO, Ti
Since the adhesive force of the inorganic surface treatment agent such as Oz is significantly improved, there is little peeling of the pigment or surface treatment agent even when the phosphor slurry is recovered and reused after the phosphor film is formed.
このように本発明によって得られた螢光体が成膜性に優
れ、顔料や無機物の表面処理剤との接着力が向上する理
由は、螢光体粒子表面に付着した４
Ｓｉの無機水酸化物が有する水酸基のため、水との親和
力が増し、従って螢光体表面の水濡れ性が良好となって
、螢光体スラリー中での螢光体の分散性がより向上する
ことと、顔料や無機物の表面処理剤の表面に存在する水
酸基と、螢光体粒子表面の水酸基との水素結合により、
相互の結合力が増すためであろうと推測される。The reason why the phosphor obtained by the present invention has excellent film-forming properties and improved adhesion to pigments and inorganic surface treatment agents is due to the inorganic hydroxide of 4-Si attached to the surface of the phosphor particles. Because of the hydroxyl groups that the substance has, its affinity with water increases, and therefore the water wettability of the surface of the phosphor improves, further improving the dispersibility of the phosphor in the phosphor slurry. Due to hydrogen bonding between the hydroxyl groups present on the surface of the surface treatment agent of inorganic materials and the hydroxyl groups on the surface of the phosphor particles,
It is presumed that this is due to an increase in mutual bonding strength.
以下、実施例により本発明を説明するが本発明はこれに
限定されるものではなく、本実施例以外の上述した原料
を用いた場合も同様の結果が得られる。The present invention will be described below with reference to Examples, but the present invention is not limited thereto, and similar results can be obtained even when the above-mentioned raw materials other than those of the Examples are used.
（実施例１〜６）
エタノール２００ｇに蒸留水１７．４ ｇと２８％アン
モニア水２２．４ ｇを溶解混合した溶液（いずれも螢
光体１５０ｇ当り）に、表１に記載の通り、平均粒径７
μｍ、比表面積０．３０ｍ２／ｇの各螢光体粒子（未処
理品）を種々の割合で添加、撹拌分散させた後、３００
ｒｐｍで回転する撹拌機で撹拌しなから２０°Ｃの恒温
槽中に保持した。なお、用５
いられる螢光体量の増減割合に応じてエタノール、蒸留
水及び２８％アンモニア水の量も増減した。(Examples 1 to 6) As shown in Table 1, average particles were added to a solution prepared by dissolving and mixing 17.4 g of distilled water and 22.4 g of 28% ammonia water in 200 g of ethanol (each per 150 g of phosphor). Diameter 7
Each phosphor particle (untreated product) with a specific surface area of 0.30 m2/g was added in various proportions, stirred and dispersed, and then
The mixture was stirred with a stirrer rotating at rpm and kept in a constant temperature bath at 20°C. Note that the amounts of ethanol, distilled water, and 28% ammonia water also increased or decreased in accordance with the rate of increase or decrease in the amount of phosphor used.
次に、２０°Ｃに調整したテトラエトキシシラン（（Ｓ
ｉ Ｏ（Ｃ２Ｈ５）、 ） ）を表１に記載の通り、
種々の割合で前記反応溶液に添加した後、２０°Ｃで２
時間保持した。次いで、所定時間経過した反応溶液を濾
過して螢光体粒子と溶液を分離し、さらに、得られた螢
光体粒子を１００°Ｃで２４時間乾燥し、螢光体粒子の
表面乙こＳｉの無機水酸化物から成る皮膜を付着させた
。Next, tetraethoxysilane ((S) adjusted to 20°C
iO(C2H5), ) ) as shown in Table 1,
After adding to the reaction solution in various proportions, 2
Holds time. Next, the reaction solution after a predetermined period of time was filtered to separate the phosphor particles from the solution, and the obtained phosphor particles were further dried at 100°C for 24 hours to remove Si on the surface of the phosphor particles. A film consisting of an inorganic hydroxide was deposited.
次にこの螢光体を純水に分散させてスラリー化し、アク
リルエマルジョンをバインダーとして公知の方法で更に
該螢光体に対しておよそ１．４重量％の割合のアルミン
酸コバルト（青色顔料）を付着させた。Next, this phosphor is dispersed in pure water to form a slurry, and using an acrylic emulsion as a binder, cobalt aluminate (blue pigment) is added in a proportion of approximately 1.4% by weight based on the phosphor using a known method. Attached.
（実施例７）
実施例２と同様にして螢光体粒子の表面にＳｉの無機水
酸化物から成る皮膜を付着させた後、その表面にアルミ
ン酸コバルト（青色顔料）に代えて該螢光体に対してお
よそ０．１重量％のアルミナ６
ゾルとチタニア（無機物の表面処理剤）を公知の方法で
付着させた。(Example 7) A film made of inorganic hydroxide of Si was attached to the surface of the phosphor particles in the same manner as in Example 2, and then the fluorescein was applied to the surface instead of cobalt aluminate (blue pigment). Approximately 0.1% by weight of alumina 6 sol and titania (an inorganic surface treatment agent) were attached to the body by a known method.
（実施例８）
未処理のＺｎＳ：Ａｇ、ＡＩ！、に代えて平均粒径１ｐ
ｍ、比表面積０．３Ｏｎ＋２／ｇのＺｎＳ：Ａｇ。(Example 8) Untreated ZnS: Ag, AI! , average particle size 1p instead of
m, ZnS:Ag with a specific surface area of 0.3On+2/g.
Ａ２螢光体粒子に公知の方法で該螢光体に対し、それぞ
れおよそ１．４重量％のアルミン酸コバルト（青色顔料
）およびおよそ０．１重量％のアルミナゾルを付着させ
た螢光体を用いる以外は実施例２と同様にしてアルミン
酸コバルト（青色顔料）及びアルミナゾル（無機物の表
面処理剤）を付着させた螢光体粒子の表面にＳｉ無機水
酸化物から成る皮膜を付着させた。Using a phosphor in which approximately 1.4% by weight of cobalt aluminate (blue pigment) and approximately 0.1% by weight of alumina sol are respectively attached to the A2 phosphor particles by a known method. A film made of Si inorganic hydroxide was deposited on the surface of the phosphor particles to which cobalt aluminate (blue pigment) and alumina sol (inorganic surface treatment agent) were deposited in the same manner as in Example 2 except for this.
（実施例９）
８、Ｏｇのテトラエトキシシランに代えて３．Ｏｇのテ
トラエトキシシランとＳｉＯ□／に２０のモル比がおよ
そ３である、３．０ｇのカリ水ガラスを用いる以外は実
施例１と同様にしてＺｎＳ：ＡｇＣｌ！、螢光体粒子の
表面にＳｉの無機水酸化物から成る皮膜を付着させ、更
にその上にこの螢光体に７
対しておよそ１．４重量％の割合のアルミン酸コバルト
（青色顔料）を付着させた。(Example 9) 8. In place of Og tetraethoxysilane, 3. ZnS:AgCl! was prepared as in Example 1, except that 3.0 g of potash water glass was used, with a molar ratio of 20 to Og tetraethoxysilane and SiO□/ of approximately 3. A film made of an inorganic hydroxide of Si was attached to the surface of the phosphor particles, and on top of this, cobalt aluminate (blue pigment) was applied to the phosphor at a ratio of approximately 1.4% by weight to 7. Attached.
（比較例１）
ＺｎＳ：Ａｇ、Ａｆｆｉ螢光体粒子表面に無機水酸化物
から成る皮膜を付着させない以外は実施例１と同様にし
て該螢光体に対しておよそ１．４重量％の割合のアルミ
ン酸コバルト（青色顔料）を付着させた。(Comparative Example 1) ZnS: Ag, Affi The ratio of approximately 1.4% by weight to the phosphor was prepared in the same manner as in Example 1 except that a film made of inorganic hydroxide was not attached to the surface of the phosphor particles. of cobalt aluminate (blue pigment) was deposited.
（比較例２）
２．０ｇのテトラエトキシシランに代えて、２．０ｇの
シランカップリング剤（ＣＨ３Ｓ ｉ （ＯＣＲ，ｌ）
３〕を用いる以外は実施例３と同様にしてＺｎＳ：Ａｇ
、Ａｆ螢光体粒子表面にＳｉ系化合物から成る皮膜と該
螢光体に対して約１．４重量％のアルミン酸コバルト（
青色顔料）を付着させた。(Comparative Example 2) Instead of 2.0 g of tetraethoxysilane, 2.0 g of silane coupling agent (CH3S i (OCR, l)
ZnS:Ag
, a film made of a Si-based compound on the surface of the Af phosphor particles and about 1.4% by weight of cobalt aluminate (based on the phosphor).
blue pigment) was attached.
（比較例３）
８．０ｇのテトラエトキシシランに代えて８．０ｇの５
ｉ０２／に２０モル比が約３であるカリ水ガラスを用い
る以外は実施例１と同様にしてＺｎＳ：Ａｇ、Ａｊ２螢
光体粒子表面にＳｉ系化合物から成８
る皮膜と該螢光体に対して約１．４重量％のアルミン酸
コバルト（青色顔料）を付着させた。(Comparative Example 3) 8.0g of 5 was replaced with 8.0g of tetraethoxysilane.
A film made of a Si-based compound was formed on the surface of the ZnS:Ag, Aj2 phosphor particles and a film formed on the phosphor was prepared in the same manner as in Example 1, except that potash water glass having a molar ratio of 20 to i02/ of about 3 was used. Cobalt aluminate (blue pigment) was deposited in an amount of about 1.4% by weight.
（比較例４）
６．０ｇのテトラエトキシシランに代えて１５ｇのテト
ラエトキシシランを用いる以外は実施例１と同様にして
ＺｎＳ：Ａｇ、Ａｆ螢光体粒子表面にＳｉの無機水酸化
物を含むＳｉ系化合物から成る皮膜と、該螢光体に対し
ておよそ０．１重量％のアルミナゾルとチタニア（無機
物の表面処理剤）を付着させた。(Comparative Example 4) ZnS:Ag, Af phosphor particles containing an inorganic hydroxide of Si on the surface were prepared in the same manner as in Example 1 except that 15 g of tetraethoxysilane was used instead of 6.0 g of tetraethoxysilane. A film made of a Si-based compound and approximately 0.1% by weight of alumina sol and titania (inorganic surface treatment agent) were attached to the phosphor.
次に上記各実施例及び比較例によって得られた夫々の螢
光体について、螢光体に付着したＳｉ系化合物からなる
皮膜の付着量（Ｓｉの重量に換算した値）、ＭＷ値、こ
の螢光体を用いて螢光膜を作成した時の螢光膜特性並び
に耐回収再生性を調べたところ、第１表に示した通りの
結果が得られた。Next, regarding each of the phosphors obtained in the above-mentioned Examples and Comparative Examples, the amount of the film made of a Si-based compound attached to the phosphor (value converted to the weight of Si), the MW value, and the phosphor value When a fluorescent film was prepared using a light material, the properties of the fluorescent film and its recovery and regeneration resistance were investigated, and the results shown in Table 1 were obtained.
なお、第１表に示した各評価項目はそれぞれ下記の評価
方法により判定した。In addition, each evaluation item shown in Table 1 was determined by the following evaluation method.
９
１）皮膜の付着量
皮膜が形成された各螢光体の表面を酸で溶解して皮膜を
剥離し、原子吸光法によりＳｉの量を定量し、その螢光
体粒子表面に付着した単位面積当りのＳｊの重量をもっ
て付着したＳｉ系化合物からなる皮膜の重量とした。9 1) Amount of film adhered The surface of each phosphor on which a film was formed was dissolved with acid, the film was peeled off, the amount of Si was determined by atomic absorption method, and the unit adhering to the surface of the phosphor particle was determined. The weight of Sj per area was taken as the weight of the film made of the deposited Si-based compound.
皮膜中におけるＳｉの無機水酸化物の有無は別途調整さ
れたこれらの化合物からなる標準試料と各螢光体につい
てＦＴ−ＩＲ（フーリエ交換赤外吸収分光法）によって
求めた吸収ピークを比較対称することによって定性的に
確認した。The presence or absence of Si inorganic hydroxide in the film is determined by comparing the absorption peaks determined by FT-IR (Fourier exchange infrared absorption spectroscopy) for each phosphor with a separately prepared standard sample made of these compounds. This was qualitatively confirmed.
２）ＭＷ値
メタノールの濃度を５容量％の間隔で変化させた水との
混合溶液を調製し、これを容積１０ｍｐ。2) MW value Prepare a mixed solution of methanol and water in which the concentration was varied at intervals of 5% by volume, and add this to a volume of 10 mp.
の試験管に５＋Ｌｌｒ入れる。次いで螢光体粒子を０゜
１〜０．２ｇ入れ、激しく振り混ぜてから静置した後観
察し、粒子全体が湿潤する最低のメタノール濃度を知り
、これをＭＷ値として表わす。例えば、” Ｍ Ｗ値２
０パとはメタノール２０容量％の混合溶液には粒子全体
が湿潤するが、メタノール２５０
容量％では粒子の一部が湿潤しないで溶液面」二に残り
浮遊する。また、“”ＭＷ値Ｏ°゛とは粒子が水のみに
対し完全に湿潤、分散することを示す。したがって、Ｍ
Ｗ値が低いほど親水性が高く水にたいし分散しやすいこ
とを示す。Put 5+Llr into the test tube. Next, 0.1 to 0.2 g of phosphor particles are added, shaken vigorously, allowed to stand, and observed. The lowest methanol concentration at which the entire particles are wetted is determined, and this is expressed as the MW value. For example, “MW value 2
0% means that in a mixed solution of 20% methanol by volume, all of the particles are wetted, but in a mixed solution of 250% methanol by volume, some of the particles are not wetted and remain suspended on the solution surface. Further, "MW value O°" indicates that the particles are completely wetted and dispersed only in water. Therefore, M
The lower the W value, the higher the hydrophilicity and the easier it is to disperse in water.
３）螢光膜の特性
各螢光体を用いてブラウン管のフェースプレート上に螢
光膜を作成してこれを目視観察し、全面がほぼ均一であ
ると認められたものを「良」と評価し、部分的にピンホ
ールやツブ（凝集粒子）が認められ、均一な膜面が得ら
れなかったものを「不良」と評価した。3) Characteristics of the fluorescent film A fluorescent film was created on the face plate of a cathode ray tube using each phosphor and visually observed, and those that were found to be almost uniform over the entire surface were evaluated as "good". However, if pinholes or lumps (agglomerated particles) were observed in some areas and a uniform film surface could not be obtained, it was rated as "poor".
４）耐回収再生性
各螢光体を７５°Ｃの１％ＮａＯＨ水溶液中で、１時間
撹拌後、デカンテーションにより水洗を繰返して、その
時の廃液中に含まれる顔料又は無機物の表面処理剤の量
を定量することによって剥離した顔料又は無機物の表面
処理剤の量を求め、顔料の場合は剥離した顔料の量が最
初の付着量の１０％より少なく、無機物の表面処理剤の
場合は剥１
離した無機物の表面処理剤の量が最初の４１着量の３０
％より少ない場合はそれぞれ、この螢光体を含むスラリ
ーから螢光体を回収する工程においても顔料や表面処理
剤の剥離は少ないと考えて耐回収再生性「良」と評価し
、上記方法で求めた顔料又は無機物の表面処理剤の剥離
量が上記値より大の場合は耐回収再生性「不良」と評価
した。4) Resistance to recovery and regeneration After stirring each phosphor in a 1% NaOH aqueous solution at 75°C for 1 hour, washing with water by decantation is repeated to remove the pigment or inorganic surface treatment agent contained in the waste liquid. The amount of peeled pigment or inorganic surface treatment agent is determined by quantifying the amount. The amount of inorganic surface treatment agent removed is 30% of the initial 41% amount.
%, it is considered that there is little peeling of the pigment or surface treatment agent during the process of recovering the phosphor from the slurry containing the phosphor, and the recovery and regeneration resistance is evaluated as "good", and the above method is used. If the determined peeling amount of the pigment or inorganic surface treatment agent was greater than the above value, the recovery and regeneration resistance was evaluated as "poor".
２
〔発明の効果〕
本発明の螢光体はこれを螢光膜とした場合、成膜性に優
れ、しかも顔料および／又は無機物の表面処理剤との接
着力が強いため、この螢光体に顔料および／又は無機物
の表面処理剤を付着させ、スラリー化したものを回収再
生した場合にも顔料および／又は無機物の表面処理剤の
剥離が少ない。2 [Effects of the Invention] When the phosphor of the present invention is used as a fluorescent film, it has excellent film-forming properties and has strong adhesion to pigments and/or inorganic surface treatment agents. Even when a pigment and/or an inorganic surface treatment agent is attached to a slurry and the slurry is recovered and recycled, there is little peeling of the pigment and/or inorganic surface treatment agent.
Claims (4)
、少なくとも一部が珪素原子に結合した水酸基を含有す
る珪素系化合物の皮膜と、顔料粒子および／又は前記珪
素系化合物以外の無機物の表面処理剤とが表面に付着し
ており、メタノールウエッタビリティー（ＭＷ値）が０
〜２０％であることを特徴とする螢光体。(1) A film of a silicon-based compound containing hydroxyl groups, at least a portion of which is bonded to silicon atoms, in an amount of 0.1 to 25 mg/m^2 in terms of the amount of silicon, and pigment particles and/or the silicon-based compound. Other inorganic surface treatment agents are attached to the surface, and the methanol wettability (MW value) is 0.
~20%.
に結合したアルコキシ基を含むことを特徴とする請求項
１に記載の螢光体。(2) The phosphor according to claim 1, wherein at least a portion of the silicon-based compound contains an alkoxy group bonded to a silicon atom.
体とを含む溶媒中に触媒を添加して上記珪素のアルコキ
サイド又はその誘導体を加水分解した後、重縮合させ、
次いで上記溶媒を除去することによって得られた螢光体
粒子の表面に顔料および／又は無機物の表面処理剤を付
着させることを特徴とする螢光体の製造方法。(3) Adding a catalyst to a solvent containing a phosphor and a silicon alkoxide or its derivative to hydrolyze the silicon alkoxide or its derivative, and then polycondensing the silicon alkoxide or its derivative;
A method for producing a phosphor, comprising: then adhering a pigment and/or an inorganic surface treatment agent to the surface of the phosphor particles obtained by removing the solvent.
着させた螢光体と珪素のアルコキサイドもしくはその誘
導体とを含む溶媒中に触媒を添加して上記珪素のアルコ
キサイド又はその誘導体を加水分解した後、重縮合させ
、次いで上記溶媒を除去することを特徴とする螢光体の
製造方法。(4) A catalyst was added to a solvent containing a phosphor with a pigment and/or an inorganic surface treatment agent attached to the surface and a silicon alkoxide or its derivative to hydrolyze the silicon alkoxide or its derivative. 1. A method for producing a phosphor, the method comprising: subsequent polycondensation, and then removing the solvent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11647390A JP2884702B2 (en) | 1989-12-26 | 1990-05-02 | Phosphor and method for producing the same |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1-337230 | 1989-12-26 | ||
| JP33723089 | 1989-12-26 | ||
| JP11647390A JP2884702B2 (en) | 1989-12-26 | 1990-05-02 | Phosphor and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03231987A true JPH03231987A (en) | 1991-10-15 |
| JP2884702B2 JP2884702B2 (en) | 1999-04-19 |
Family
ID=26454799
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11647390A Expired - Fee Related JP2884702B2 (en) | 1989-12-26 | 1990-05-02 | Phosphor and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2884702B2 (en) |
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|---|---|---|---|---|
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