JP2003201473A - Zinc oxide-silica inorganic porous fluorescent body and method of producing the same - Google Patents
Zinc oxide-silica inorganic porous fluorescent body and method of producing the sameInfo
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- JP2003201473A JP2003201473A JP2002312132A JP2002312132A JP2003201473A JP 2003201473 A JP2003201473 A JP 2003201473A JP 2002312132 A JP2002312132 A JP 2002312132A JP 2002312132 A JP2002312132 A JP 2002312132A JP 2003201473 A JP2003201473 A JP 2003201473A
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- Prior art keywords
- zinc
- silica
- inorganic porous
- based inorganic
- zinc oxide
- Prior art date
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、シリカゲル等のシ
リカ系無機多孔質体に酸化亜鉛微粒子を内包させた蛍光
体に関するものである。より詳しくは、安定性、ハンド
リング性等の粉体特性に優れ、かつ経済性にも優れた応
用範囲が広い無機蛍光体及びその製造方法に関する。TECHNICAL FIELD The present invention relates to a phosphor in which fine particles of zinc oxide are included in a silica-based inorganic porous material such as silica gel. More specifically, the present invention relates to an inorganic phosphor having excellent powder properties such as stability and handling property and also being economical, and having a wide range of applications, and a method for producing the same.
【０００２】[0002]
【特許文献１】 特許第３１９５０５４号公報[Patent Document 1] Japanese Patent No. 3195054
【特許文献２】 特開平５−１１７６５４号公報[Patent Document 2] Japanese Patent Laid-Open No. 5-117654
【特許文献３】 特開平５−２０９１７３号公報[Patent Document 3] Japanese Unexamined Patent Publication No. 5-209173
【特許文献４】 特開平５−３１０４３２号公報[Patent Document 4] Japanese Patent Laid-Open No. 5-310432
【特許文献５】 特開２００１−２３３６１２号公報[Patent Document 5] Japanese Patent Laid-Open No. 2001-233612
【０００３】無機蛍光体の代表的なものには、蛍光灯な
どに使用されているハロリン酸カルシウムをはじめ、ア
ルカリハライド、酸化物、酸素酸塩、フッ化物等の各種
化合物のものがあり、それらにＭｎやＳｂを賦活体とし
て添加した賦活型蛍光体もある。また、その蛍光体及び
製造方法に関しては、既に数多くの技術が知られてい
る。Typical examples of inorganic phosphors include calcium halophosphates used in fluorescent lamps and various compounds such as alkali halides, oxides, oxyacid salts, and fluorides. There is also an activated phosphor in which Mn or Sb is added as an activator. Many techniques are already known for the phosphor and the manufacturing method.
【０００４】それらの中で酸化亜鉛とシリカ系無機多孔
質体、特にシリカを含有する蛍光体としては、特許文献
１が開示する短い減衰時間を有するマンガンをドープし
た珪酸亜鉛に基づく蛍光材料に関するものがあり、その
蛍光材料は酸化亜鉛、シリカゲル及び炭酸マンガンから
なる水性懸濁液を乾燥させ、得られた乾燥物をオーブン
中で処理する方法で製造される。また、特許文献２に
は、低速電子線励起蛍光体として使用される発光輝度が
高くなるＺｎＯ：Ｚｎ蛍光体において、金属亜鉛粉末微
粒子の表面に、シリカを被着した金属亜鉛粉末を、Ｚｎ
Ｏ：Ｚｎ蛍光体に混合又は付着することが開示されてい
る。Among them, a phosphor containing zinc oxide and a silica-based inorganic porous material, particularly silica, relates to a phosphor material based on manganese-doped zinc silicate having a short decay time disclosed in Patent Document 1. The fluorescent material is produced by drying an aqueous suspension of zinc oxide, silica gel and manganese carbonate and treating the resulting dried product in an oven. Further, in Patent Document 2, in a ZnO: Zn phosphor used as a slow-electron-beam-excited phosphor and having a high emission brightness, metal zinc powder coated with silica is added to the surface of fine particles of the metal zinc powder.
It is disclosed to be mixed or attached to an O: Zn phosphor.
【０００５】このほかにも、特許文献３には、可溶性コ
バルト塩と可溶性亜鉛塩とを含む水溶液に沈澱剤を添加
し、共沈物を乾燥させた後、酸化珪素を混合し焼成した
ＣｏＯ・ＺｎＯ・ＳｉＯ2系青色顔料を青色発光蛍光体
の表面に付着してなる顔料付青色発光蛍光体、特許文献
４には、コロイダルシリカ及びコバルトと亜鉛を含む水
溶液にアルカリ水溶液を添加し、生成した共沈混合物を
乾燥し焼成した青色顔料を青色発光蛍光体の表面に付着
してなる顔料付青色発光蛍光体が開示されている。さら
に、最近では、ソーコナイト型結晶構造を有するマンガ
ン含有ケイ酸亜鉛を焼成して相転移させたウィレマイト
型結晶構造のマンガン含有ケイ酸亜鉛あるいはそのシリ
カ複合体からなる蛍光体が特許文献５に開示されてい
る。In addition to this, in Patent Document 3, a precipitant is added to an aqueous solution containing a soluble cobalt salt and a soluble zinc salt, the coprecipitate is dried, and then silicon oxide is mixed and baked into CoO. A pigmented blue light emitting phosphor in which a ZnO.SiO 2 based blue pigment is adhered to the surface of a blue light emitting phosphor. In Patent Document 4, an alkaline aqueous solution is added to an aqueous solution containing colloidal silica and cobalt and zinc. A pigmented blue light-emitting phosphor is disclosed in which a blue pigment obtained by drying and firing a coprecipitation mixture is attached to the surface of the blue light-emitting phosphor. Further, recently, Patent Document 5 discloses a phosphor comprising a manganese-containing zinc silicate having a willemite-type crystal structure obtained by firing a manganese-containing zinc silicate having a sauconite-type crystal structure to cause a phase transition, or a silica composite thereof. ing.
【０００６】[0006]
【発明が解決しようとする課題】以上のとおり、酸化亜
鉛とシリカとを含有する蛍光体及びその製造方法につい
ても、既に各種のものが提案されているが、それらの方
法は製造プロセスが煩雑であり、また特殊な限られた用
途においては使用が可能であっても、汎用の無機蛍光体
として使用するに至っていない。そのため粉体特性や経
済性に優れ、様々な用途において使用可能な無機蛍光体
の開発が嘱望されている。As described above, various phosphors containing zinc oxide and silica and methods for producing the same have already been proposed. However, these methods require complicated production processes. In addition, even though it can be used for special limited applications, it has not yet been used as a general-purpose inorganic phosphor. Therefore, development of an inorganic phosphor that is excellent in powder properties and economical and can be used in various applications is desired.
【０００７】このような事情に鑑み、本発明者らは従来
の製造方法にとらわれることなく、新たな手法にてシリ
カゲル等のシリカ系無機多孔質体を利用する蛍光体を製
造すべく鋭意研究を重ね、その結果開発に成功したのが
本発明である。したがって、本発明の課題は、安定性、
ハンドリング性等の粉体特性に優れ、さらに経済性にも
優れた応用範囲が広いシリカゲル等のシリカ系無機多孔
質体を利用する蛍光体及びその製造方法を提供すること
にある。In view of such circumstances, the inventors of the present invention have conducted diligent research to produce a phosphor using a silica-based inorganic porous material such as silica gel by a new method without being restricted by the conventional production method. The present invention has been succeeded in repeated development as a result. Therefore, the problem of the present invention is stability,
It is an object of the present invention to provide a phosphor using a silica-based inorganic porous material such as silica gel, which has excellent powder characteristics such as handleability and is economical and has a wide range of applications, and a method for producing the same.
【０００８】[0008]
【課題を解決するための手段】本発明は、シリカ系無機
多孔質蛍光体及びその製造方法を提供するものであり、
そのうち前者は、シリカ系無機多孔質体の細孔内に酸化
亜鉛微粒子を内包したことを特徴とする。また、後者の
製造方法は、シリカ系無機多孔質体の細孔内に亜鉛イオ
ン又は亜鉛化合物を導入し、酸化雰囲気下で加熱焼成す
ることを特徴とするものである。The present invention provides a silica-based inorganic porous phosphor and a method for producing the same.
The former is characterized in that zinc oxide fine particles are included in the pores of the silica-based inorganic porous material. The latter production method is characterized in that zinc ions or a zinc compound are introduced into the pores of the silica-based inorganic porous material and the mixture is heated and baked in an oxidizing atmosphere.
【０００９】そして、本発明では、酸化雰囲気の下で加
熱焼成により亜鉛イオン又は亜鉛化合物を酸化せしめる
ものであり、その際共存する有機鎖や陰イオン基を分解
し、シリカゲル等のシリカ系無機多孔質体の細孔を利用
してシリカ系無機多孔質体中に酸化亜鉛微粒子（ナノ粒
子）を分散した状態で存在させることにより、酸化亜鉛
の有する蛍光作用を効率良く発現するものである。Further, in the present invention, zinc ions or zinc compounds are oxidized by heating and baking in an oxidizing atmosphere, at which time coexisting organic chains and anionic groups are decomposed, and silica-based inorganic porous materials such as silica gel are used. By allowing the zinc oxide fine particles (nanoparticles) to exist in a dispersed state in the silica-based inorganic porous body by utilizing the pores of the porous body, the fluorescent effect of zinc oxide is efficiently exhibited.
【００１０】また、得られるシリカ系無機多孔質蛍光体
は、微細なナノ粒子である酸化亜鉛微粒子がそれより大
きなシリカ系無機多孔質蛍光体内に内包されているので
安定性、ハンドリング性等に優れている。その結果、該
多孔質蛍光体は、従来の蛍光体に比較し、製造が容易で
あり経済性に優れるため、オプトエレクトロニクス材料
のみならず特殊塗料、インキ、絵の具、化粧品、紙等の
汎用の無機蛍光体として利用できるという利点がある。Further, the obtained silica-based inorganic porous phosphor is excellent in stability, handleability, etc. because zinc oxide fine particles which are fine nanoparticles are contained in a larger silica-based inorganic porous phosphor. ing. As a result, the porous phosphor is easier to manufacture and more economical than conventional phosphors, and is therefore a general-purpose inorganic material for not only optoelectronic materials but also special paints, inks, paints, cosmetics, and paper. It has the advantage that it can be used as a phosphor.
【００１１】[0011]
【発明の実施の形態】以下に、本発明の実施の形態につ
いて詳細に説明するが、本発明は、それによって何ら限
定されるものではなく、特許請求の範囲の記載によって
特定されるものであることはいうまでもない。本発明
は、前述のとおりシリカ系無機多孔質体の細孔内に酸化
亜鉛微粒子を内包したことを特徴とする酸化亜鉛−シリ
カ系無機多孔質蛍光体及びその製造方法であり、その製
造方法は、シリカ系無機多孔質体の細孔内に亜鉛イオン
又は亜鉛化合物を導入し、酸化雰囲気下で加熱焼成する
ことを特徴とするものである。BEST MODE FOR CARRYING OUT THE INVENTION The embodiments of the present invention will be described in detail below, but the present invention is not limited thereby and is specified by the description of the scope of claims. Needless to say. The present invention is a zinc oxide-silica inorganic porous phosphor and a method for producing the same, characterized in that zinc oxide fine particles are included in the pores of the silica-based inorganic porous body as described above, and the method for producing the same. It is characterized in that zinc ions or a zinc compound are introduced into the pores of the silica-based inorganic porous material and heated and baked in an oxidizing atmosphere.
【００１２】本発明で使用するシリカ系無機多孔質体に
ついては、亜鉛化合物溶液を細孔内に内包できるもので
れば特に制限されることなく使用可能であり、シリカゲ
ルやメソポーラスシリカ、その他の多孔質シリカ又は珪
酸塩などを用いることができる。珪酸塩としては、ゼオ
ライトや珪酸カルシウム、層状珪酸塩などが使用でき
る。The silica-based inorganic porous material used in the present invention can be used without particular limitation as long as it can enclose the zinc compound solution in the pores, and silica gel, mesoporous silica, and other porous materials can be used. Silica or silicate can be used. As the silicate, zeolite, calcium silicate, layered silicate or the like can be used.
【００１３】それらのなかでも、シリカゲルは、細孔分
布がシャープで、かつ種々の細孔径をもつものが比較的
簡便に調製できるばかりでなく、屈折率が比較的低い物
質であるため、蛍光発光のために必要な励起光の吸収が
少なく、また内包された酸化亜鉛から発した蛍光も吸収
しにくいため、より効率的な蛍光体とすることができ、
本発明で用いるシリカ系無機多孔質体としては最適であ
る。Among them, silica gel has a sharp pore distribution and various pore diameters, and can be prepared relatively easily, and since it has a relatively low refractive index, it emits fluorescence. The absorption of the excitation light required for is low, and since the fluorescence emitted from the encapsulated zinc oxide is also difficult to be absorbed, a more efficient phosphor can be obtained,
It is most suitable as the silica-based inorganic porous material used in the present invention.
【００１４】また、使用されるシリカ系無機多孔質体の
粒径や平均細孔径については、亜鉛化合物溶液を細孔内
に内包できるものでれば特に制限されることはなく、蛍
光体の用途に応じて、適宜選択すればよい。ただ、細孔
径に関しては、小さすぎる場合、亜鉛化合物の導入に長
時間を要したり、亜鉛化合物を導入して焼成し蛍光体と
した際に、その発光が弱くなるといった傾向が認められ
る。したがって、使用するシリカ系無機多孔質体は、窒
素吸着測定による平均細孔径が１ｎｍ以上、より望まし
くは３ｎｍ以上であることがよい。The particle size and average pore size of the silica-based inorganic porous material used are not particularly limited as long as the zinc compound solution can be included in the pores, and the use of the phosphor It may be appropriately selected according to However, with respect to the pore size, when the pore size is too small, it tends to take a long time to introduce the zinc compound, or when the zinc compound is introduced and fired to form a phosphor, its emission tends to be weak. Therefore, the silica-based inorganic porous material to be used preferably has an average pore diameter of 1 nm or more, more preferably 3 nm or more as measured by nitrogen adsorption.
【００１５】そのシリカ系無機多孔質体の平均細孔径の
上限については、内包された酸化亜鉛微粒子がナノ状態
を維持でき、本発明の酸化亜鉛−シリカ系無機多孔質蛍
光体の特徴である、酸化亜鉛バルク体の蛍光よりも高エ
ネルギー（短波長）側で発光を示すような範囲であれば
よい。ただ、細孔径が大きすぎる場合、亜鉛化合物導入
後の焼成の際に、焼成温度や焼成時間などの焼成条件に
よっては、酸化亜鉛微粒子の成長が促進され、大きな酸
化亜鉛粒子となってしまう傾向も認められる。この場
合、酸化亜鉛バルク体と同じような蛍光波長を示す蛍光
体となってしまい、本発明の蛍光体の特徴が発現しない
こともあるので、より望ましくは、使用するシリカ系無
機多孔質体の平均細孔径は、５００ｎｍ以下であるのが
よい。Regarding the upper limit of the average pore diameter of the silica-based inorganic porous material, the zinc oxide fine particles contained therein can maintain the nano state, which is a feature of the zinc oxide-silica-based inorganic porous fluorescent material of the present invention. The range may be such that light is emitted on the higher energy (shorter wavelength) side than the fluorescence of the zinc oxide bulk material. However, if the pore size is too large, during the firing after the introduction of the zinc compound, depending on the firing conditions such as the firing temperature and the firing time, the growth of the zinc oxide fine particles is promoted, and there is a tendency that the zinc oxide particles become large. Is recognized. In this case, since it becomes a phosphor having a fluorescence wavelength similar to that of the zinc oxide bulk body, the characteristics of the phosphor of the present invention may not be expressed. Therefore, more desirably, the silica-based inorganic porous body used is The average pore diameter is preferably 500 nm or less.
【００１６】本発明で使用されるシリカゲル等のシリカ
系無機多孔質体は、上述のとおり細孔を有するため、空
気中の水分や有機物を吸着しやすいという性質がある。
そのため使用に際しては２００℃程度の温度で予め乾燥
して、細孔内に吸着している水分や有機物を取り除いて
おくことが望ましく、この操作を真空下で行なうことが
より望ましい。こうすることにより、亜鉛化合物を効率
よく細孔内に導入することが可能となる。Since the silica-based inorganic porous material such as silica gel used in the present invention has pores as described above, it has a property of easily adsorbing moisture and organic substances in the air.
Therefore, in use, it is desirable to dry in advance at a temperature of about 200 ° C. to remove water and organic substances adsorbed in the pores, and it is more desirable to carry out this operation under vacuum. By doing so, it becomes possible to efficiently introduce the zinc compound into the pores.
【００１７】シリカ系無機多孔質体の細孔内に亜鉛イオ
ン又は亜鉛化合物を導入する際の手法についても特に限
定されないが、可溶性亜鉛塩の溶液に、シリカ系無機多
孔質体を浸漬する方法が最も簡便であり、特に真空下で
浸漬する方法がより効率よく亜鉛化合物を細孔内に導入
することができ好適である。その際、浸漬する溶液の溶
媒については亜鉛塩が溶解すればよく、水や各種の有機
溶媒等が使用でき、特に制限はないが、亜鉛塩が溶解し
やすく、かつ入手が容易で扱いやすい液体である水やエ
タノールが適しているといえる。The method for introducing zinc ions or zinc compounds into the pores of the silica-based inorganic porous material is not particularly limited, but a method of immersing the silica-based inorganic porous material in a solution of a soluble zinc salt is available. The simplest method is preferable, and the method of immersing in a vacuum is particularly preferable because the zinc compound can be introduced into the pores more efficiently. At that time, as for the solvent of the solution to be immersed, it suffices that the zinc salt be dissolved, water and various organic solvents can be used, and there is no particular limitation, but the zinc salt is easily dissolved, and the liquid that is easily available and easy to handle It can be said that water and ethanol are suitable.
【００１８】また、使用する溶媒に対する亜鉛化合物の
溶解度についてみると、溶解度が高いほうが濃度の高い
亜鉛化合物溶液を調製でき、１回の処理でシリカ系無機
多孔質体の細孔内に導入できる亜鉛イオン又は亜鉛化合
物量を多くすることができる。しかし、溶解度が高すぎ
ると、亜鉛化合物溶液の濃度は高くできるものの、亜鉛
イオン又は亜鉛化合物の導入率が低くなる傾向にある。
この場合、使用した亜鉛化合物のうちの極僅かしかシリ
カ系無機多孔質体の細孔内に導入することができないこ
とになる。したがって、使用する溶媒は、使用する亜鉛
化合物の溶解度が適切な範囲であることが望ましく、特
にアルコールは一般的な亜鉛化合物の溶解度が１〜２０
ｇ／Ｌ程度で、使用する亜鉛化合物をより効率よくシリ
カ系無機多孔質体の細孔内に導入できる点で、最も望ま
しいものである。Regarding the solubility of the zinc compound in the solvent used, a zinc compound solution having a higher solubility can be prepared with a higher solubility, and zinc which can be introduced into the pores of the silica-based inorganic porous material by one treatment. The amount of ionic or zinc compounds can be increased. However, if the solubility is too high, the concentration of the zinc compound solution can be increased, but the introduction rate of zinc ions or zinc compounds tends to be low.
In this case, only a very small amount of the zinc compound used can be introduced into the pores of the silica-based inorganic porous material. Therefore, it is desirable that the solvent used has a solubility of the zinc compound used in an appropriate range, and particularly alcohol has a solubility of a general zinc compound of 1 to 20.
It is the most desirable in that the zinc compound to be used can be introduced into the pores of the silica-based inorganic porous material more efficiently at about g / L.
【００１９】シリカ系無機多孔質体の細孔内に酸化亜鉛
微粒子を形成するために使用する可溶性亜鉛塩について
は、溶媒に溶解し、加熱により酸化亜鉛を形成するもの
であれば特に制限されることなく各種の亜鉛塩が使用可
能である。それには、酢酸亜鉛、硫酸亜鉛、硝酸亜鉛、
塩化亜鉛等の各種の可溶性塩があり、それら化合物を溶
解する溶媒にあわせて溶解しやすいものを適宜選択すれ
ばよい。中でも酢酸亜鉛は、導入後の焼成に際して酸化
による分解温度が低く焼成に要するエネルギーを低く押
さえられ、また焼成に際して有害ガスも発生しないばか
りでなく、比較的分子サイズが小さいことからより効率
よくシリカ系無機多孔質体の細孔内に亜鉛を導入するこ
とができ好適である。The soluble zinc salt used to form the zinc oxide fine particles in the pores of the silica-based inorganic porous material is not particularly limited as long as it dissolves in a solvent and forms zinc oxide by heating. Various zinc salts can be used without any. It includes zinc acetate, zinc sulfate, zinc nitrate,
There are various types of soluble salts such as zinc chloride, and those which are easily dissolved may be appropriately selected according to the solvent in which these compounds are dissolved. Among them, zinc acetate is more efficient because it has a low decomposition temperature due to oxidation during firing after introduction and can suppress energy required for firing to a low level, does not generate harmful gas during firing, and has a relatively small molecular size. It is preferable because zinc can be introduced into the pores of the inorganic porous body.
【００２０】また、亜鉛化合物の導入量に関しては、蛍
光体として求められる特性に応じて適宜調節することが
できる。具体的には、亜鉛化合物の導入量を増やして、
シリカ系無機多孔質体の細孔内に内包される酸化亜鉛微
粒子の粒子数を多くすることにより、蛍光発光強度を高
めることができる。さらに、亜鉛化合物の導入量を調節
して、内包される酸化亜鉛微粒子のサイズをコントロー
ルすることにより、所望の蛍光波長を有する蛍光体とす
ることもできる。The amount of the zinc compound introduced can be appropriately adjusted according to the characteristics required of the phosphor. Specifically, by increasing the amount of zinc compound introduced,
The fluorescence emission intensity can be increased by increasing the number of zinc oxide fine particles included in the pores of the silica-based inorganic porous material. Furthermore, by adjusting the amount of zinc compound introduced to control the size of the zinc oxide fine particles to be encapsulated, a phosphor having a desired fluorescence wavelength can be obtained.
【００２１】細孔内に導入された亜鉛化合物は、イオン
あるいは分子状態であると考えられるが、それらは酸化
雰囲気下で加熱焼成して酸化亜鉛にする必要がある。加
熱焼成は大気中でよいが、大気中より酸素濃度の高い雰
囲気であれば、酸化反応が進みやすくなおよい。その際
の加熱温度は、使用する亜鉛化合物の種類によって適宜
調節することが望ましい。The zinc compound introduced into the pores is considered to be in an ionic or molecular state, but they must be heated and calcined in an oxidizing atmosphere to form zinc oxide. The heating and firing may be performed in the air, but an atmosphere having a higher oxygen concentration than that in the air is more preferable because the oxidation reaction easily proceeds. It is desirable that the heating temperature at that time be appropriately adjusted according to the type of zinc compound used.
【００２２】具体的には、使用する亜鉛化合物が分解し
酸化物に変化する温度以上が良い。一般に工業薬品とし
て用いられる亜鉛化合物の分解温度は、３００℃以上で
あることを考慮すると、本発明においては、焼成の温度
を３００℃以上とすることがより好適である。使用する
亜鉛化合物の種類別に、より具体的に述べると、酢酸亜
鉛を用いた場合には３５０℃以上、硫酸亜鉛を用いた場
合には７００℃以上、塩化亜鉛を用いた場合には７５０
℃以上とすることが望ましい。Specifically, the temperature is preferably higher than the temperature at which the zinc compound used is decomposed and converted into an oxide. Considering that the decomposition temperature of a zinc compound generally used as an industrial chemical is 300 ° C. or higher, in the present invention, the firing temperature is more preferably 300 ° C. or higher. More specifically, each type of zinc compound used is 350 ° C. or higher when zinc acetate is used, 700 ° C. or higher when zinc sulfate is used, and 750 ° C. when zinc chloride is used.
It is desirable to set the temperature above ℃.
【００２３】また、焼成温度の上限については、特段の
制約はなく、焼成装置の種類や、焼成に供する亜鉛化合
物を導入したシリカ系無機多孔質体の重量、焼成時間等
を勘案して、導入した亜鉛化合物がより効率よく酸化亜
鉛の状態に変化するように調節すればよい。ただし、８
００℃を超えると、使用するシリカ系無機多孔質体の焼
結が進み、蛍光体としての性状や粉体としての性状を維
持できない恐れもあるので、より望ましくは８００℃以
下での焼成がよい。The upper limit of the firing temperature is not particularly limited, and is introduced in consideration of the type of firing apparatus, the weight of the silica-based inorganic porous material into which the zinc compound used for firing is introduced, the firing time, and the like. The zinc compound may be adjusted so as to more efficiently change into a zinc oxide state. However, 8
If the temperature exceeds 00 ° C, the silica-based inorganic porous material to be used may be sintered, and the properties as a phosphor or powder may not be maintained. Therefore, it is more preferable to fire at 800 ° C or lower. .
【００２４】このようにして作製された酸化亜鉛−シリ
カ系無機多孔質蛍光体は、亜鉛内包量の増加に伴って比
表面積、平均細孔径、細孔容積が減少する傾向が見られ
る。これはシリカゲル細孔内に酸化亜鉛が入り込んだこ
とを示唆している。本発明の酸化亜鉛−シリカ系無機多
孔質蛍光体は、３５０〜５５０ｎｍ付近に発光ピークを
有しており、酸化亜鉛バルク体の発光領域５００〜６０
０ｎｍに比較し短波長で、高エネルギーの蛍光を発す
る。In the zinc oxide-silica based inorganic porous phosphor thus produced, the specific surface area, average pore diameter and pore volume tend to decrease as the amount of zinc contained increases. This suggests that zinc oxide has entered the silica gel pores. The zinc oxide-silica based inorganic porous phosphor of the present invention has an emission peak in the vicinity of 350 to 550 nm, and the emission region 500 to 60 of the zinc oxide bulk body.
It emits high-energy fluorescence at a shorter wavelength than 0 nm.
【００２５】また、本発明においては、使用するシリカ
系無機多孔質体の細孔径及び／または酸化亜鉛の内包量
を調節することによって、蛍光波長を３５０〜５５０ｎ
ｍの範囲でコントロールすることができる。すなわち、
平均細孔径の大きいシリカ系無機多孔質体を使用するこ
とにより、蛍光発光ピークをより長波長側にシフトさせ
ることができる。この現象については、シリカ系無機多
孔質体の細孔内に内包されている酸化亜鉛の粒径が大き
くなり、酸化亜鉛バルク体により近くなることに起因し
ていると本発明者らは考えている。In the present invention, the fluorescence wavelength is adjusted to 350 to 550 n by adjusting the pore size of the silica-based inorganic porous material used and / or the amount of zinc oxide included.
It can be controlled in the range of m. That is,
By using a silica-based inorganic porous material having a large average pore diameter, the fluorescence emission peak can be shifted to the longer wavelength side. The present inventors believe that this phenomenon is caused by the fact that the particle size of zinc oxide contained in the pores of the silica-based inorganic porous material is increased and is closer to the zinc oxide bulk material. There is.
【００２６】使用するシリカ系無機多孔質体の平均細孔
径と蛍光波長との関係について具体例を挙げると、シリ
カ系無機多孔質体として平均細孔径が７．８ｎｍ、３９
ｎｍのシリカゲルを使用し、亜鉛内包量を約４５ｍｇ／
ｇとした場合、７．８ｎｍのものでは４３０ｎｍ付近に
蛍光ピークが出現するのに対して、３９ｎｍのものでは
４４０ｎｍ付近に蛍光ピークが現れる。つまり、平均細
孔径が小さい方が蛍光波長はより短波長側となり、逆に
平均細孔径が大きいほうが長波長側に蛍光ピークを有す
ることとなる。Specific examples of the relationship between the average pore diameter of the silica-based inorganic porous material used and the fluorescence wavelength are given below. As the silica-based inorganic porous material, the average pore diameter is 7.8 nm and 39.
nm silica gel is used, and the zinc inclusion amount is about 45 mg /
In the case of g, a fluorescence peak appears near 430 nm in the case of 7.8 nm, whereas a fluorescence peak appears near 440 nm in the case of 39 nm. That is, the smaller the average pore diameter is, the shorter the fluorescence wavelength is, and the larger the average pore diameter is, the larger the fluorescence wavelength is on the long wavelength side.
【００２７】さらに、亜鉛化合物の導入量を調節し、シ
リカ系無機多孔質体の細孔内に内包される酸化亜鉛量を
コントロールすることによっても、任意の蛍光発光ピー
クを有する蛍光体を作製することができる。亜鉛化合物
の導入量を調節するには、シリカ系無機多孔質体に亜鉛
化合物を導入する際の両者の量比を変えてやればよい。
つまり、亜鉛化合物の導入を、シリカ系無機多孔質体を
可溶性亜鉛塩の溶液に浸漬することにより行う場合は、
可溶性亜鉛塩の溶液の濃度を上げたり、シリカ系無機多
孔質体に対する可溶性亜鉛塩の溶液の量を増やすことに
よって、亜鉛化合物の導入量を多くすることができる。Further, by adjusting the amount of the zinc compound introduced and controlling the amount of zinc oxide contained in the pores of the silica-based inorganic porous material, a phosphor having an arbitrary fluorescence emission peak is produced. be able to. The amount of the zinc compound introduced can be adjusted by changing the ratio of the two amounts when the zinc compound is introduced into the silica-based inorganic porous material.
That is, when the introduction of the zinc compound is performed by immersing the silica-based inorganic porous body in the solution of the soluble zinc salt,
The amount of the zinc compound introduced can be increased by increasing the concentration of the solution of the soluble zinc salt or by increasing the amount of the solution of the soluble zinc salt in the silica-based inorganic porous material.
【００２８】亜鉛導入量と蛍光波長との関係について具
体例を挙げると、比表面積が約４８９ｍ2／ｇ、細孔容
積が１．４８ｍＬ／ｇ、平均細孔径が１３．６ｎｍのシ
リカゲルをシリカ系無機多孔質体に使用し、それに対し
て亜鉛内包量を、２９．０ｍｇ／ｇ、５６．８ｍｇ／ｇ
としたものの蛍光測定におけるピーク波長は、それぞれ
約４２０ｎｍ、４７０ｎｍとなる。As a specific example of the relationship between the amount of zinc introduced and the fluorescence wavelength, silica gel having a specific surface area of about 489 m 2 / g, a pore volume of 1.48 mL / g and an average pore diameter of 13.6 nm is used as a silica-based material. It is used for inorganic porous materials, and the zinc inclusion amount is 29.0 mg / g, 56.8 mg / g
However, the peak wavelengths in the fluorescence measurement are about 420 nm and 470 nm, respectively.
【００２９】つまり、酸化亜鉛の内包量が多い場合はよ
り長波長側、逆に内包量が少ない場合はより短波長側の
蛍光を発する蛍光体を得ることができる。この現象につ
いても、先に述べた細孔径の場合と同様に、シリカ系無
機多孔質体の細孔内に内包されている酸化亜鉛の粒径に
関連しており、酸化亜鉛内包量が多い際にはその粒径は
大きくなり、内包量が少ない際には粒径が小さくなるこ
とに起因すると本発明者らは考えている。That is, when the inclusion amount of zinc oxide is large, it is possible to obtain a fluorescent substance which emits fluorescence on the longer wavelength side, and conversely, when the inclusion amount of zinc oxide is small, a fluorescent substance which emits fluorescence on the shorter wavelength side can be obtained. This phenomenon is also related to the particle size of zinc oxide contained in the pores of the silica-based inorganic porous material, as in the case of the pore size described above, and when the zinc oxide inclusion amount is large. The inventors believe that this is because the particle size becomes large and the particle size becomes small when the amount of inclusion is small.
【００３０】また、平均細孔径の異なる２種以上のシリ
カ系無機多孔質体を混合して使用することにより、２以
上の蛍光ピークをもつような蛍光体としたり、各々の細
孔径に起因する蛍光波長の平均的な波長位置にピークを
有する蛍光体とすることもできる。そのほかにも、細孔
分布が広範にわたるようなシリカ系無機多孔質体を使用
すれば、蛍光スペクトル（蛍光波長の分布）も広範にわ
たるような蛍光体を得ることもできる。Further, by mixing and using two or more kinds of silica-based inorganic porous materials having different average pore diameters, a phosphor having two or more fluorescence peaks can be obtained, or the phosphors can be caused by the respective pore diameters. It is also possible to use a phosphor having a peak at an average wavelength position of the fluorescence wavelength. In addition, if a silica-based inorganic porous material having a wide pore distribution is used, it is possible to obtain a phosphor having a wide fluorescence spectrum (distribution of fluorescence wavelength).
【００３１】本発明によれば、簡単な工程で酸化亜鉛微
粒子をシリカゲルなどの無機多孔質体の細孔に内包でき
る。その結果、酸化亜鉛微粒子は、より粒子径の大きな
シリカゲル等の多孔質体の細孔に内包され、安定性、ハ
ンドリング性等の粉体特性に優れたものとなり、経済性
にも優れた応用範囲が広い無機蛍光体を製造することが
できる。こうして得られた蛍光体は、オプトエレクトロ
ニクス分野をはじめ、特殊塗料、インキ、絵の具、樹
脂、化粧品、紙の機能性填料や顔料等として幅広い用途
において有効に活用でき、産業上の利用価値が高いとい
う特徴を有している。According to the present invention, zinc oxide fine particles can be encapsulated in the pores of an inorganic porous material such as silica gel by a simple process. As a result, the zinc oxide fine particles are encapsulated in the pores of a porous material such as silica gel having a larger particle diameter, and have excellent powder properties such as stability and handling properties, and are also economically applicable. Inorganic phosphors having a wide range can be manufactured. The phosphor thus obtained can be effectively used in a wide range of applications including optoelectronics fields, special paints, inks, paints, resins, cosmetics, functional fillers and pigments for paper, and has a high industrial utility value. It has features.
【００３２】[0032]
【実施例】本発明について、実施例をあげて更に具体的
に説明するが、本発明は、該実施例によって何等限定さ
れるものではなく、特許請求の範囲の記載によって特定
されるものであることはいうまでもない。EXAMPLES The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples and is specified by the description of the claims. Needless to say.
【００３３】[実施例１]シリカゲル（富士シリシア化学
社製ＳＹＬＯＳＰＨＥＲＥ、粒径３〜５μｍの球状粒
子、比表面積４８６ｍ2／ｇ）を２００℃で４時間真空
加熱乾燥させ、シリカゲル孔内に存在する水分や有機物
を除去した。得られたシリカゲル試料２．０ｇを、真空
雰囲気において５００ｍｌのビーカーに入れ、その中に
酢酸亜鉛のエタノール溶液（酢酸亜鉛量で１．０ｇ／
Ｌ）５００ｍｌを添加し、試料を浸漬させた。[Example 1] Silica gel (SYLOSPHERE manufactured by Fuji Silysia Chemical Ltd., spherical particles having a particle size of 3 to 5 µm, specific surface area 486 m 2 / g) was vacuum-dried at 200 ° C for 4 hours to be present in the silica gel pores. Water and organic substances were removed. 2.0 g of the obtained silica gel sample was placed in a 500 ml beaker in a vacuum atmosphere, and an ethanol solution of zinc acetate (1.0 g / zinc acetate was added).
L) 500 ml was added and the sample was immersed.
【００３４】得られたシリカゲル試料分散懸濁液を２４
時間撹拌して、シリカゲル孔内へ酢酸亜鉛吸着を行なっ
た。この試料分散液を窒素ガスで加圧ろ過した後、蒸留
水で試料を洗浄してシリカゲル外表面に吸着している酢
酸亜鉛を除去した。得られた亜鉛導入シリカゲル試料を
乾燥後、加熱炉で４００℃、４時間焼成し、酢酸亜鉛に
由来するシリカゲル中に含まれる有機鎖を燃焼酸化させ
て、酸化亜鉛−シリカ系無機多孔質蛍光体を得た。The resulting silica gel sample dispersion suspension was added to 24
After stirring for a period of time, zinc acetate was adsorbed into the silica gel pores. This sample dispersion liquid was filtered under pressure with nitrogen gas, and then the sample was washed with distilled water to remove zinc acetate adsorbed on the outer surface of the silica gel. The obtained zinc-introduced silica gel sample is dried and then fired in a heating furnace at 400 ° C. for 4 hours to burn and oxidize the organic chains contained in the silica gel derived from zinc acetate to give a zinc oxide-silica inorganic porous phosphor. Got
【００３５】[実施例２及び３]酢酸亜鉛エタノール溶液
中の酢酸亜鉛の濃度を、それぞれ２．０ｇ／Ｌ、５．０
ｇ／Ｌとした以外は、実施例１と同様にして酸化亜鉛−
シリカ系無機多孔質蛍光体を得た。[Examples 2 and 3] The concentrations of zinc acetate in the zinc acetate ethanol solution were 2.0 g / L and 5.0, respectively.
Zinc oxide-in the same manner as in Example 1 except that g / L was used.
A silica-based inorganic porous phosphor was obtained.
【００３６】[実施例４]シリカゲル（富士シリシア化学
社製ＳＹＬＯＳＰＨＥＲＥ、粒径３〜５μｍの球状粒
子、比表面積４８６ｍ2／ｇ）を２００℃で４時間真空
加熱乾燥させ、シリカゲル孔内に存在する水分や有機物
を除去した。得られたシリカゲル試料２．０ｇを、真空
雰囲気において５００ｍｌのビーカーに入れ、その中に
酢酸亜鉛水溶液（酢酸亜鉛量で７．５ｇ／Ｌ）５００
ｍｌを添加し、試料を浸漬させた。Example 4 Silica gel (SYLOSPHERE manufactured by Fuji Silysia Chemical Ltd., spherical particles having a particle size of 3 to 5 μm, specific surface area of 486 m 2 / g) was vacuum-dried at 200 ° C. for 4 hours to be present in the silica gel pores. Water and organic substances were removed. 2.0 g of the obtained silica gel sample was placed in a 500 ml beaker in a vacuum atmosphere, and 500 g of zinc acetate aqueous solution (7.5 g / L in terms of zinc acetate) was placed therein.
ml was added and the sample was immersed.
【００３７】得られたシリカゲル試料分散懸濁液を２４
時間撹拌して、シリカゲル孔内へ酢酸亜鉛吸着を行なっ
た。この試料分散液を窒素ガスで加圧ろ過した後、蒸留
水で試料を洗浄してシリカゲル外表面に吸着している酢
酸亜鉛を除去した。得られた亜鉛導入シリカゲル試料を
乾燥後、加熱炉で４００℃、４時間焼成し、酢酸亜鉛に
由来するシリカゲル中に含まれる有機鎖を燃焼酸化させ
て酸化亜鉛−シリカ系無機多孔質蛍光体を得た。The resulting silica gel sample dispersion suspension was added to 24
After stirring for a period of time, zinc acetate was adsorbed into the silica gel pores. This sample dispersion liquid was filtered under pressure with nitrogen gas, and then the sample was washed with distilled water to remove zinc acetate adsorbed on the outer surface of the silica gel. The obtained zinc-introduced silica gel sample was dried and then baked in a heating furnace at 400 ° C. for 4 hours to burn and oxidize the organic chains contained in the silica gel derived from zinc acetate to obtain a zinc oxide-silica-based inorganic porous phosphor. Obtained.
【００３８】[実施例５]シリカゲル（富士シリシア化学
社製ＣＡＲｉＡＣＴ Ｑ−１０、粒径 １００μｍの球
状粒子、比表面積２６９ｍ2／ｇ）を２００℃で４時間
真空加熱乾燥させ、シリカゲル孔内に存在する水分や有
機物を除去した。その後、真空雰囲気において５００ｍ
ｌのビーカーにシリカゲル試料２．０ｇを移し、その中
に酢酸亜鉛のエタノール溶液（酢酸亜鉛量で１．０ｇ／
Ｌ）５００ ｍｌを添加し、試料を浸漬させた。Example 5 Silica gel (CARiACT Q-10 manufactured by Fuji Silysia Chemical Ltd., spherical particles having a particle size of 100 μm, specific surface area of 269 m 2 / g) was vacuum-dried at 200 ° C. for 4 hours to be present in the silica gel pores. The water and organic matter that existed were removed. After that, 500m in a vacuum atmosphere
A 2.0 g silica gel sample was transferred to a 1-liter beaker, and an ethanol solution of zinc acetate (1.0 g / zinc acetate was added).
L) 500 ml was added and the sample was immersed.
【００３９】得られたシリカゲル試料分散懸濁液を２４
時間撹拌して、シリカゲル孔内へ酢酸亜鉛吸着を行なっ
た。この試料分散液を窒素ガスで加圧ろ過した後、蒸留
水で試料を洗浄してシリカゲル外表面に吸着している酢
酸亜鉛を除去した。得られたシリカゲル試料を乾燥後、
加熱炉で４００℃、４時間焼成し、酢酸亜鉛に由来する
シリカゲル中に含まれる有機鎖を燃焼酸化させて、酸化
亜鉛−シリカ系無機多孔質蛍光体を得た。The resulting silica gel sample dispersion suspension was added to 24
After stirring for a period of time, zinc acetate was adsorbed into the silica gel pores. This sample dispersion liquid was filtered under pressure with nitrogen gas, and then the sample was washed with distilled water to remove zinc acetate adsorbed on the outer surface of the silica gel. After drying the obtained silica gel sample,
It was baked at 400 ° C. for 4 hours in a heating furnace, and the organic chain contained in the silica gel derived from zinc acetate was burned and oxidized to obtain a zinc oxide-silica based inorganic porous phosphor.
【００４０】[実施例６]酢酸亜鉛エタノール溶液中の酢
酸亜鉛の濃度を５．０ｇ／Ｌとした以外は、実施例５と
同様にして酸化亜鉛−シリカ系無機多孔質蛍光体を得
た。Example 6 A zinc oxide-silica based inorganic porous phosphor was obtained in the same manner as in Example 5 except that the concentration of zinc acetate in the zinc acetate ethanol solution was 5.0 g / L.
【００４１】[実施例７]シリカゲル（富士シリシア化学
社製ＣＡＲｉＡＣＴ Ｑ−１０、粒径 ３２〜１５０μ
ｍの球状粒子、比表面積２６０ｍ2／ｇ）を２００℃で
４時間真空加熱乾燥させ、シリカゲル孔内に存在する水
分や有機物を除去した。その後、１０００ｍｌのビーカ
ーにシリカゲル試料４．０ｇを移し、その中に酢酸亜鉛
水溶液（酢酸亜鉛量で９．０ｇ／Ｌ）５００ ｍｌを添
加し、試料を浸漬させた。Example 7 Silica gel (CARiACT Q-10 manufactured by Fuji Silysia Chemical Ltd., particle size 32 to 150 μm)
m spherical particles and a specific surface area of 260 m 2 / g) were vacuum dried at 200 ° C. for 4 hours to remove water and organic substances existing in the silica gel pores. Thereafter, 4.0 g of the silica gel sample was transferred to a 1000 ml beaker, and 500 ml of an aqueous zinc acetate solution (9.0 g / L in terms of zinc acetate) was added to the beaker to immerse the sample.
【００４２】得られたシリカゲル試料分散懸濁液を２４
時間撹拌して、シリカゲル孔内へ酢酸亜鉛吸着を行なっ
た。この試料分散液をろ過した後、蒸留水で試料を洗浄
してシリカゲル外表面に吸着している酢酸亜鉛を除去し
た。得られたシリカゲル試料を乾燥後、加熱炉で４００
℃、４時間焼成し、酢酸亜鉛に由来するシリカゲル中に
含まれる有機鎖を燃焼酸化させて、酸化亜鉛−シリカ系
無機多孔質蛍光体を得た。The resulting silica gel sample dispersion suspension was added to 24
After stirring for a period of time, zinc acetate was adsorbed into the silica gel pores. After filtering this sample dispersion, the sample was washed with distilled water to remove the zinc acetate adsorbed on the outer surface of the silica gel. After drying the obtained silica gel sample, 400 in a heating furnace
The mixture was baked at 4 ° C. for 4 hours, and the organic chain contained in the silica gel derived from zinc acetate was burned and oxidized to obtain a zinc oxide-silica inorganic porous phosphor.
【００４３】[実施例８]酢酸亜鉛水溶液中の酢酸亜鉛の
濃度を１００ｇ／Ｌとした以外は、実施例７と同様にし
て酸化亜鉛−シリカ系無機多孔質蛍光体を得た。Example 8 A zinc oxide-silica based inorganic porous phosphor was obtained in the same manner as in Example 7 except that the concentration of zinc acetate in the zinc acetate aqueous solution was 100 g / L.
【００４４】[実施例９]シリカゲル（富士シリシア化学
社製ＣＡＲｉＡＣＴ Ｇ−１０、平均粒径 ３μｍの破
砕状粒子、比表面積３７６ｍ2／ｇ）を２００℃で４時
間真空加熱乾燥させ、シリカゲル孔内に存在する水分や
有機物を除去した。その後、１０００ｍｌのビーカーに
シリカゲル試料４．０ｇを移し、その中に酢酸亜鉛水溶
液（酢酸亜鉛量で４９ｇ／Ｌ）５００ ｍｌを添加し、
試料を浸漬させた。Example 9 Silica gel (CARiACT G-10 manufactured by Fuji Silysia Chemical Ltd., crushed particles having an average particle size of 3 μm, specific surface area of 376 m 2 / g) was vacuum-dried at 200 ° C. for 4 hours, and the silica gel pores were dried. The water and organic substances existing in the water were removed. Then, 4.0 g of the silica gel sample was transferred to a 1000 ml beaker, and 500 ml of an aqueous zinc acetate solution (49 g / L in terms of zinc acetate) was added to the beaker.
The sample was immersed.
【００４５】得られたシリカゲル試料分散懸濁液を２４
時間撹拌して、シリカゲル孔内へ酢酸亜鉛吸着を行なっ
た。この試料分散液をろ過した後、蒸留水で試料を洗浄
してシリカゲル外表面に吸着している酢酸亜鉛を除去し
た。得られたシリカゲル試料を乾燥後、加熱炉で４００
℃、４時間焼成し、酢酸亜鉛に由来するシリカゲル中に
含まれる有機鎖を燃焼酸化させて、酸化亜鉛−シリカ系
無機多孔質蛍光体を得た。The obtained silica gel sample dispersion suspension was added to 24
After stirring for a period of time, zinc acetate was adsorbed into the silica gel pores. After filtering this sample dispersion, the sample was washed with distilled water to remove the zinc acetate adsorbed on the outer surface of the silica gel. After drying the obtained silica gel sample, 400 in a heating furnace
The mixture was baked at 4 ° C. for 4 hours, and the organic chain contained in the silica gel derived from zinc acetate was burned and oxidized to obtain a zinc oxide-silica inorganic porous phosphor.
【００４６】[実施例１０]シリカゲル（富士シリシア化
学社製ＣＡＲｉＡＣＴ Ｑ−３０、粒径 １００μｍの
球状粒子、比表面積１１１ｍ2／ｇ）を２００℃で４時
間真空加熱乾燥させ、シリカゲル孔内に存在する水分や
有機物を除去した。その後、真空雰囲気において５００
ｍｌのビーカーにシリカゲル試料２．０ｇを移し、その
中に酢酸亜鉛のエタノール溶液（酢酸亜鉛量で５．０ｇ
／Ｌ）５００ ｍｌを添加し、試料を浸漬させた。Example 10 Silica gel (CARiACT Q-30, manufactured by Fuji Silysia Chemical Ltd., spherical particles having a particle size of 100 μm, specific surface area 111 m 2 / g) was vacuum-dried at 200 ° C. for 4 hours, and was present in the silica gel pores. The water and organic matter that existed were removed. Then, in a vacuum atmosphere, 500
Transfer 2.0 g of the silica gel sample to a beaker of ml, and add ethanol solution of zinc acetate (5.0 g of zinc acetate in the solution).
/ L) 500 ml was added and the sample was immersed.
【００４７】得られたシリカゲル試料分散懸濁液を２４
時間撹拌して、シリカゲル孔内へ酢酸亜鉛吸着を行なっ
た。この試料分散液を窒素ガスで加圧ろ過した後、蒸留
水で試料を洗浄してシリカゲル外表面に吸着している酢
酸亜鉛を除去した。得られたシリカゲル試料を乾燥後、
加熱炉で４００℃、４時間焼成し、酢酸亜鉛に由来する
シリカゲル中に含まれる有機鎖を燃焼酸化させて、酸化
亜鉛−シリカ系無機多孔質蛍光体を得た。The obtained silica gel sample dispersion suspension was added to 24
After stirring for a period of time, zinc acetate was adsorbed into the silica gel pores. This sample dispersion liquid was filtered under pressure with nitrogen gas, and then the sample was washed with distilled water to remove zinc acetate adsorbed on the outer surface of the silica gel. After drying the obtained silica gel sample,
It was baked at 400 ° C. for 4 hours in a heating furnace, and the organic chain contained in the silica gel derived from zinc acetate was burned and oxidized to obtain a zinc oxide-silica based inorganic porous phosphor.
【００４８】[実施例１１]酢酸亜鉛エタノール溶液中の
酢酸亜鉛の濃度を２．０ｇ／Ｌとした以外は、実施例５
と同様にして酸化亜鉛−シリカ系無機多孔質蛍光体を得
た。Example 11 Example 5 except that the concentration of zinc acetate in the ethanol solution of zinc acetate was 2.0 g / L.
A zinc oxide-silica based inorganic porous phosphor was obtained in the same manner as in.
【００４９】[作製蛍光体等の各種物性評価]実施例で作
製した酸化亜鉛−シリカ系無機多孔質蛍光体等に関し各
種の物性測定を行った。具体的には、各実施例で作製し
た酸化亜鉛−シリカ系無機多孔質蛍光体及び実施例で使
用したシリカゲルに関し、亜鉛内包量、比表面積、平均
細孔径及び細孔容積を測定した。また、それらに加えて
実施例で作製した酸化亜鉛−シリカ系無機多孔質蛍光体
のうち一部について、電子顕微鏡観察及び蛍光測定を行
った。それらの結果は電子顕微鏡観察及び蛍光測定を除
き表１に示した。[Evaluation of various physical properties of manufactured phosphor, etc.] Various physical properties of the zinc oxide-silica based inorganic porous phosphor manufactured in the examples were measured. Specifically, with respect to the zinc oxide-silica-based inorganic porous phosphor produced in each example and the silica gel used in the examples, the zinc inclusion amount, the specific surface area, the average pore diameter and the pore volume were measured. In addition, in addition to them, some of the zinc oxide-silica-based inorganic porous phosphors produced in the examples were subjected to electron microscope observation and fluorescence measurement. The results are shown in Table 1 except for electron microscope observation and fluorescence measurement.
【００５０】[0050]
【表１】 [Table 1]
【００５１】これらの物性評価に使用した測定装置は、
以下のものである。
亜鉛内包量の測定：原子吸光分光測定（セイコー電子工
業社製、SAS7500）
比表面積及び平均細孔径測定：窒素吸着測定（島津製作
所製、GEMINI2360）
表面性状観察及び粒径測定：走査型電子顕微鏡（日本電
子社製、JSM-6100）
蛍光測定：蛍光分光測定（日立製作所製、F-4010）
紫外光吸収端測定：ＤＲ−ＵＶ測定（島津製作所製、UV
-3100）The measuring device used for the evaluation of these physical properties is
It is as follows. Measurement of zinc content: Atomic absorption spectrophotometry (Seiko Denshi Kogyo, SAS7500) Specific surface area and average pore size measurement: Nitrogen adsorption measurement (Shimadzu, GEMINI2360) Surface observation and particle size measurement: Scanning electron microscope ( JEOL, JSM-6100) Fluorescence measurement: Fluorescence spectrophotometry (Hitachi, F-4010) UV absorption edge measurement: DR-UV measurement (Shimadzu, UV
-3100)
【００５２】[比表面積、平均細孔径、細孔容積等の測
定結果]表１によれば、使用するシリカ系無機多孔質体
が同じものについてみると、亜鉛内包量は酢酸亜鉛溶液
の濃度の上昇と共に増加しており、酢酸亜鉛溶液の濃度
を変化させることにより、亜鉛内包量を調節できること
がわかる。また、水溶液を使用した実施例４は、エタノ
ール溶液を使用した実施例３より亜鉛濃度は高いにもか
かわらず亜鉛内包量が低く、溶媒に水を使用すると、エ
タノールを使用した場合より亜鉛内包の効率は低下する
といえる。さらに、比表面積、平均細孔径、細孔容積
は、酸化亜鉛内包前のシリカゲルに比し、酸化亜鉛が内
包された酸化亜鉛−シリカ系無機多孔質蛍光体の方が減
少しており、かつその内包量の増加に伴ってより減少し
ている。[Measurement Results of Specific Surface Area, Average Pore Diameter, Pore Volume, etc.] According to Table 1, when the same silica-based inorganic porous material is used, the amount of zinc inclusion depends on the concentration of the zinc acetate solution. It increases with an increase, and it can be seen that the amount of zinc inclusion can be adjusted by changing the concentration of the zinc acetate solution. In addition, Example 4 using an aqueous solution has a lower zinc encapsulation amount than Example 3 using an ethanol solution, although the zinc content is low. It can be said that efficiency decreases. Furthermore, the specific surface area, the average pore diameter, the pore volume, compared with the silica gel before inclusion of zinc oxide, zinc oxide encapsulated zinc oxide-silica-based inorganic porous phosphor is reduced, and It decreases more as the amount of inclusion increases.
【００５３】[電子顕微鏡観察]実施例３において、酢酸
亜鉛エタノール溶液（酢酸亜鉛濃度を５ｇ／Ｌ）を用い
て作製した酸化亜鉛−シリカ系無機多孔質蛍光体と、そ
の蛍光体作製に使用したシリカゲルのＳＹＬＯＳＰＨＥ
ＲＥとを走査型電子顕微鏡にて比較観察したところ、酸
化亜鉛内包前後でのシリカゲルの粒子の形状、粒径には
変化は見られず、酸化亜鉛内包シリカゲルの表面、外部
には酸化亜鉛粒子は観察されなかった。この事実及び前
記した比表面積、平均細孔径及び細孔容積が、いずれも
酸化亜鉛の内包量の増加に伴って減少している事実よ
り、ほぼ全ての酸化亜鉛がシリカゲル細孔内に存在して
いると判断できる。[Electron Microscope Observation] In Example 3, a zinc oxide-silica based inorganic porous phosphor prepared using a zinc acetate ethanol solution (zinc acetate concentration: 5 g / L) and the phosphor were prepared. SYLOSPHE of silica gel
As a result of comparative observation with RE with a scanning electron microscope, no change was found in the shape and particle size of the silica gel particles before and after inclusion of zinc oxide, and zinc oxide particles were observed on the surface of the zinc oxide-encapsulated silica gel and outside. Not observed. From this fact and the fact that the specific surface area, the average pore diameter, and the pore volume described above all decrease with an increase in the inclusion amount of zinc oxide, almost all zinc oxide is present in the silica gel pores. You can judge that
【００５４】[蛍光特性の評価]蛍光分光測定装置を使用
して、蛍光測定を行なった。励起波長は２５０ｎｍ（光
源：キセノンランプ）、測定波長範囲は３００〜６００
ｎｍ、試料は固体用セルに装填し、圧粉体状にしたもの
を用いた。測定結果を図１ないし５に示す。いずれの試
料も酸化亜鉛バルク体の蛍光波長領域である５００〜６
００ｎｍよりも短波長の蛍光を発していることがわか
る。[Evaluation of Fluorescence Property] Fluorescence measurement was performed using a fluorescence spectrometer. Excitation wavelength is 250 nm (light source: xenon lamp), measurement wavelength range is 300 to 600
nm, the sample was loaded in a cell for solid and made into a powder compact. The measurement results are shown in FIGS. All samples are in the fluorescent wavelength region of zinc oxide bulk body, which is 500 to 6
It can be seen that it emits fluorescence with a wavelength shorter than 00 nm.
【００５５】使用したシリカゲルが同じで、亜鉛導入量
の異なる実施例１〜３で作製した蛍光体の測定結果（図
１）についてみると、亜鉛導入量の比較的少ない実施例
１及び２の蛍光体では、４３０ｎｍ付近に発光ピークが
出現するのに対して、亜鉛導入量の多い実施例３の試料
では、４７０ｎｍ付近に発光のピークが出現する。ま
た、実施例５と６（図２）、又は実施例７と８（図３）
とを比較しても、亜鉛内包量の多い方がより長波長側に
蛍光波長を有することがわかる。Looking at the measurement results (FIG. 1) of the phosphors produced in Examples 1 to 3 in which the silica gel used was the same and the amount of zinc introduced was different, the fluorescence of Examples 1 and 2 in which the amount of zinc introduced was relatively small. In the body, an emission peak appears near 430 nm, whereas in the sample of Example 3 in which the amount of zinc introduced is large, an emission peak appears near 470 nm. Also, Examples 5 and 6 (FIG. 2) or Examples 7 and 8 (FIG. 3)
Comparing with the above, it can be seen that the one having a larger amount of zinc inclusion has the fluorescence wavelength on the longer wavelength side.
【００５６】亜鉛導入量がほぼ等しく、使用したシリカ
ゲルの平均細孔径の異なる実施例１０（図５）及び実施
例１１（図６）の蛍光測定結果を見ると、使用したシリ
カゲルの平均細孔径が小さい実施例１１では４３０ｎｍ
付近に蛍光ピークが出現するのに対して、平均細孔径が
大きい実施例１０では、実施例２よりも長波長側の４４
０ｎｍ付近に蛍光ピークを有することがわかる。このこ
とは、使用するシリカ系無機多孔質体の平均細孔径によ
り蛍光波長の調節ができることを表している。Looking at the fluorescence measurement results of Example 10 (FIG. 5) and Example 11 (FIG. 6) in which the amounts of zinc introduced were almost the same and the average pore sizes of the silica gel used were different, it was found that the average pore size of the silica gel used was 430 nm for small Example 11
In contrast to the appearance of a fluorescence peak in the vicinity, in Example 10 having a large average pore diameter, 44 on the longer wavelength side than Example 2 was used.
It can be seen that it has a fluorescence peak near 0 nm. This means that the fluorescence wavelength can be controlled by the average pore diameter of the silica-based inorganic porous material used.
【００５７】[0057]
【発明の効果】本発明の酸化亜鉛−シリカ系無機多孔質
蛍光体は、無機蛍光体としてこれまでにない優れた特性
を有している。すなわち、微細粒子の酸化亜鉛がそれよ
り大きく、安定なシリカ系無機多孔質内に内包されてお
り、その結果、蛍光体は、安定性、ハンドリング性等の
粉体特性に優れたものとなっており、かつ、経済性にも
優れた応用範囲が広いものとなっている。Industrial Applicability The zinc oxide-silica based inorganic porous phosphor of the present invention has excellent properties as never before available as an inorganic phosphor. That is, the zinc oxide fine particles are larger than that, and are encapsulated in a stable silica-based inorganic porous material, and as a result, the phosphor has excellent powder characteristics such as stability and handling property. In addition, it has a wide range of applications with excellent economical efficiency.
【００５８】また、その製造方法は、含浸、焼成という
簡単な工程で酸化亜鉛微粒子をシリカゲルなどのシリカ
系無機多孔質体の細孔内に内包させるという経済性に優
れた方法である。そして、得られた無機蛍光体はオプト
エレクトロニクス分野をはじめ、特殊塗料、インキ、絵
の具、樹脂、化粧品、紙の機能性填料や顔料等として有
効に活用することが期待でき、産業上の利用価値が高い
という特徴を有している。Further, the production method is an economical method in which zinc oxide fine particles are included in the pores of a silica-based inorganic porous material such as silica gel by a simple process of impregnation and firing. And the obtained inorganic phosphor can be expected to be effectively used as a functional filler or pigment in the optoelectronic field, special paints, inks, paints, resins, cosmetics, paper, etc., and has industrial utility value. It has the characteristic of being expensive.
【図１】 実施例１、２、３で作製した蛍光体、及びシ
リカゲル（ＳＹＬＯＳＰＨＥＲＥ）における蛍光の波長
と強度を測定した結果を示すグラフである。FIG. 1 is a graph showing the results of measuring the wavelength and intensity of fluorescence in a phosphor prepared in Examples 1, 2, and 3 and silica gel (SYLOSPHERE).
【図２】 実施例５、６で作製した蛍光体、及び使用し
たシリカゲル（ＣＡＲｉＡＣＴ Ｑ−１０）における蛍
光の波長と強度を測定した結果を示すグラフである。FIG. 2 is a graph showing the results of measuring the wavelength and intensity of fluorescence in the phosphors produced in Examples 5 and 6 and the silica gel (CARiACT Q-10) used.
【図３】 実施例７、８で作製した蛍光体、及び使用し
たシリカゲル(ＣＡＲｉＡＣＴ Ｑ−１０)における蛍光
波長と強度を測定した結果を示すグラフである。FIG. 3 is a graph showing the results of measuring the fluorescence wavelength and intensity of the phosphors produced in Examples 7 and 8 and the silica gel (CARiACT Q-10) used.
【図４】 実施例９で作製した蛍光体、及び使用したシ
リカゲル(ＣＡＲｉＡＣＴ Ｇ−１０)における蛍光波長
と強度を測定した結果を示すグラフである。FIG. 4 is a graph showing the results of measuring the fluorescence wavelength and intensity of the phosphor prepared in Example 9 and the silica gel (CARiACT G-10) used.
【図５】 実施例１０で作製した蛍光体、及び使用した
シリカゲル(ＣＡＲｉＡＣＴ Ｑ−３０)における蛍光波
長と強度を測定した結果を示すグラフである。FIG. 5 is a graph showing the results of measuring the fluorescence wavelength and intensity of the phosphor prepared in Example 10 and the silica gel (CARiACT Q-30) used.
【図６】 実施例１１で作製した蛍光体、及び使用した
シリカゲル(ＣＡＲｉＡＣＴ Ｑ−１０)における蛍光波
長と強度を測定した結果を示すグラフである。FIG. 6 is a graph showing the results of measuring the fluorescence wavelength and intensity of the phosphor prepared in Example 11 and the silica gel (CARiACT Q-10) used.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 武井 孝 神奈川県相模原市上溝1517−２ (72)発明者 田辺 克幸 東京都西多摩郡日の出町平井８−１ 日鉄 鉱業株式会社内 (72)発明者 鵜籠 敦 東京都西多摩郡日の出町平井８−１ 日鉄 鉱業株式会社内 (72)発明者 糟谷 滋 東京都西多摩郡日の出町平井８−１ 日鉄 鉱業株式会社内 (72)発明者 三觜 幸平 東京都西多摩郡日の出町平井８−１ 日鉄 鉱業株式会社内 Ｆターム(参考） 4H001 CA02 CC05 XA08 XA30 ─────────────────────────────────────────────────── ─── Continued front page (72) Inventor Takashi Takei 1517-2 Kamimizo, Sagamihara City, Kanagawa Prefecture (72) Inventor Katsuyuki Tanabe 8-1, Hirai, Hinode-cho, Nishitama-gun, Tokyo Mining Co., Ltd. (72) Inventor Atsushi Ugo 8-1, Hirai, Hinode-cho, Nishitama-gun, Tokyo Mining Co., Ltd. (72) Inventor Shigeru Kasuya 8-1, Hirai, Hinode-cho, Nishitama-gun, Tokyo Mining Co., Ltd. (72) Inventor Kohei Mikami 8-1, Hirai, Hinode-cho, Nishitama-gun, Tokyo Mining Co., Ltd. F-term (reference) 4H001 CA02 CC05 XA08 XA30
Claims (10)
鉛微粒子を内包したことを特徴とする酸化亜鉛−シリカ
系無機多孔質蛍光体。1. A zinc oxide-silica based inorganic porous phosphor, characterized in that zinc oxide fine particles are included in the pores of the silica based inorganic porous body.
る請求項１に記載の酸化亜鉛−シリカ系無機多孔質蛍光
体。2. The zinc oxide-silica based inorganic porous phosphor according to claim 1, wherein the silica based inorganic porous body is silica gel.
よる平均細孔径が１ｎｍ以上である請求項１又は２に記
載の酸化亜鉛−シリカ系無機多孔質蛍光体。3. The zinc oxide-silica based inorganic porous phosphor according to claim 1 or 2, wherein the silica based inorganic porous body has an average pore diameter of 1 nm or more as measured by nitrogen adsorption.
オン又は亜鉛化合物を導入し、酸化雰囲気下で加熱焼成
することを特徴とする酸化亜鉛−シリカ系無機多孔質蛍
光体の製造方法。4. A method for producing a zinc oxide-silica based inorganic porous phosphor, which comprises introducing zinc ions or a zinc compound into the pores of the silica based inorganic porous material, and heating and firing in an oxidizing atmosphere. .
イオン又は亜鉛化合物の導入が、該多孔質体を可溶性亜
鉛塩の溶液に浸漬することによりなされるものである請
求項４に記載の酸化亜鉛−シリカ系無機多孔質蛍光体の
製造方法。5. The method according to claim 4, wherein the zinc ion or the zinc compound is introduced into the pores of the silica-based inorganic porous material by immersing the porous material in a solution of a soluble zinc salt. A method for producing the described zinc oxide-silica based inorganic porous phosphor.
る請求項４又は５に記載の酸化亜鉛−シリカ系無機多孔
質蛍光体の製造方法。6. The method for producing a zinc oxide-silica based inorganic porous phosphor according to claim 4, wherein the silica based inorganic porous body is silica gel.
を溶媒とするものである請求項４、５又は６に記載の酸
化亜鉛−シリカ系無機多孔質蛍光体の製造方法。7. The method for producing a zinc oxide-silica inorganic porous phosphor according to claim 4, 5 or 6, wherein the solution of the soluble zinc salt uses ethanol or water as a solvent.
ないし７のいずれか１項に記載の酸化亜鉛−シリカ系無
機多孔質蛍光体の製造方法。8. The soluble zinc salt is zinc acetate.
8. A method for producing a zinc oxide-silica based inorganic porous phosphor according to any one of items 1 to 7.
る請求項４ないし８のいずれか１項に記載の酸化亜鉛−
シリカ系無機多孔質蛍光体の製造方法。9. The zinc oxide according to claim 4, wherein the heating and firing is performed at a temperature of 300 ° C. or higher.
A method for producing a silica-based inorganic porous phosphor.
又は酸化亜鉛微粒子の内包量を変化させることにより、
蛍光波長を調節することを特徴とする、請求項４ないし
９のいずれか１項に記載の酸化亜鉛−シリカ系無機多孔
質蛍光体の製造方法。10. A pore diameter of a silica-based inorganic porous material and / or
Or by changing the inclusion amount of zinc oxide fine particles,
The method for producing a zinc oxide-silica based inorganic porous phosphor according to any one of claims 4 to 9, wherein the fluorescence wavelength is adjusted.
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