JP3396443B2 - Luminescent fluorescent glass ceramics - Google Patents

Luminescent fluorescent glass ceramics

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Publication number
JP3396443B2
JP3396443B2 JP11274299A JP11274299A JP3396443B2 JP 3396443 B2 JP3396443 B2 JP 3396443B2 JP 11274299 A JP11274299 A JP 11274299A JP 11274299 A JP11274299 A JP 11274299A JP 3396443 B2 JP3396443 B2 JP 3396443B2
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JP
Japan
Prior art keywords
glass
mol
afterglow
ceramics
phosphorescent
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
JP11274299A
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Japanese (ja)
Other versions
JP2000281382A (en
Inventor
杰 傅
康雄 越智
進 上原
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ohara Inc
Original Assignee
Ohara Inc
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Priority to JP11274299A priority Critical patent/JP3396443B2/en
Priority to US09/398,593 priority patent/US6287993B1/en
Publication of JP2000281382A publication Critical patent/JP2000281382A/en
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Publication of JP3396443B2 publication Critical patent/JP3396443B2/en
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C4/00—Compositions for glass with special properties
    • C03C4/12—Compositions for glass with special properties for luminescent glass; for fluorescent glass
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
    • C03C10/0009—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing silica as main constituent

Description

【発明の詳細な説明】Detailed Description of the Invention

【０００１】[0001]

【発明の属する技術分野】本発明は光の照射による残光
特性を有し、しかも残光輝度が高く残光時間が長く、残
光色が多様な、新規蓄光性蛍光ガラスセラミックスに関
するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel phosphorescent fluorescent glass ceramic which has afterglow characteristics by irradiation of light, has high afterglow brightness, long afterglow time, and various afterglow colors. .

【０００２】[0002]

【従来の技術】蛍光とは、外部からの刺激（励起）によ
って物質が可視域付近の光を発する現象であり、 蛍光
灯、放電ランプ、ＣＲＴ（Ｃａｔｈｏｄ Ｒａｙ Ｔｕ
ｂｅ）いわゆるブラウン管などの発光がこれを用いてい
る。蛍光を発する物質を蛍光体というが、励起停止後に
目に感じられる程度の時間（０．１秒程度以上）の蛍光
が続く場合、これを燐光と呼び、さらに燐光の続く時間
（すなわち残光時間）が室温で数時間に及ぶような長残
光性を持つ蛍光体を、蓄光性蛍光体と呼んでいる。2. Description of the Related Art Fluorescence is a phenomenon in which a substance emits light in the visible range due to an external stimulus (excitation). Fluorescent lamps, discharge lamps, CRTs (Cathode Ray Tu)
be) This is used for light emission of so-called cathode ray tubes. A substance that emits fluorescence is called a fluorophore. When fluorescence continues for a time (0.1 seconds or more) that can be perceived by the eye after excitation is stopped, this is called phosphorescence, and the time after phosphorescence (that is, afterglow time) ) Is a phosphor having a long afterglow at room temperature for several hours is called a phosphorescent phosphor.

【０００３】このような蓄光性蛍光体としては硫化物系
と酸化物系が知られている。ＺｎＳ：Ｃｕは数十年前に
実用化された代表的な硫化物系蓄光性蛍光体である。し
かし残光時間がせいぜい３時間程度で短いという問題点
があり、更に日光に含まれる紫外線と大気中に含まれる
水分により、ＺｎＳ＋Ｈ2Ｏ→ＺｎＯ＋Ｈ2Ｓの形に分解
され、蛍光体粒子自体が黒化し、これに伴い残光輝度も
低下するため、短期間で著しい機能低下を生じるという
欠点を持っている。そのため、これら蓄光体は主に夜光
時計や屋内の夜間表示など、非常に限られた用途に限定
されていた。Sulfide-based and oxide-based phosphors are known as such phosphorescent phosphors. ZnS: Cu is a typical sulfide-based phosphorescent phosphor that was put into practical use several decades ago. However, there is a problem that the afterglow time is as short as about 3 hours at most, and further, it is decomposed into a form of ZnS + H 2 O → ZnO + H 2 S by ultraviolet rays contained in the sunlight and water contained in the atmosphere, and the phosphor particles themselves. Since it blackens and the afterglow luminance decreases accordingly, there is a drawback that the function is remarkably deteriorated in a short period of time. For this reason, these phosphors have been limited to very limited applications such as a luminous clock and an indoor night display.

【０００４】一方、酸化物系の中で代表的な蓄光性蛍光
体としてｍ（Ｓｒ1-XＥｕX）・ｎＡｌ2Ｏ3・ｙＢ2Ｏ3：
中国特許ＣＮ１０５３８０７Ａ、Ｓｒ1-xＡｌ2Ｏ4-x：
Ｅｕx、Ｌｎy：特開平８―１２７７７２、（Ｚｎ1-X-Y
ＭｇXＭｎY）Ｏ・ｎ（Ｇａ1-ZＡｌZ）2Ｏ3：特開平１０
−８８１２６、ｍ（Ｓｒ1-aＭ1 a）Ｏ・ｎ（Ｍｇ
1-bＭ2 b）Ｏ・２（Ｓｉ1-cＧｅc）Ｏ2：Ｅｕx、Ｌｎy：
特開平９−１９４８３３が報告されている。これらの蓄
光性蛍光体は残光輝度が高く、さらに残光時間も長いと
いう特徴に加えて、化学耐久性、耐光性に優れるという
特性を持っている。そのため、これらの蛍光体は既存の
夜光時計や屋内の夜間表示などの狭い用途の以外に、防
災標識、位置認識用危険防止の表示、装飾品等への幅広
い用途も期待される。しかし、これら既存の蓄光性蛍光
体は全て従来の焼結法により作製されたセラミックス
（焼結体）であって、製造過程が煩雑で、しかも蛍光体
自体が透明なものが得難い。On the other hand, a typical phosphorescent fluorescent among oxides
M as body (Sr1-XEuX) ・ NAl2O3・ YB2O3:
Chinese Patent CN1053807A, Sr1-xAl2O4-x:
Eux, Lny: JP-A-8-127772, (Zn1-XY
MgXMnY) O ・ n (Ga1-ZAlZ)2O3: Japanese Patent Laid-Open No. Hei 10
-88126, m (Sr1-aM1 a) O ・ n (Mg
1-bM2 b) O ・ 2 (Si1-cGec) O2: Eux, Lny:
JP-A-9-194833 has been reported. These accumulations
Photoluminescent phosphors have high afterglow brightness and long afterglow time.
In addition to these features, it has excellent chemical durability and light resistance.
It has characteristics. Therefore, these phosphors are
In addition to narrow applications such as night clocks and indoor night displays,
Wide range of signs for disasters, indication of danger for position recognition, decorations, etc.
It is also expected to have many uses. However, these existing phosphorescent fluorescent
All bodies are ceramics produced by conventional sintering method
(Sintered body), the manufacturing process is complicated, and the phosphor is
It's hard to get something transparent.

【０００５】[0005]

【発明が解決しようとする課題】本発明は、残光輝度が
高く残光時間も長く、化学耐久性、耐光性に優れるとい
う特性を備えた上でなおかつ、製造過程が簡単で、成形
性に富み、不透明なものはもちろん、透明なものでも容
易に作製できる蓄光性蛍光ガラスセラミックスを提供す
るものである。DISCLOSURE OF THE INVENTION The present invention has the characteristics of high afterglow brightness, long afterglow time, excellent chemical durability and light resistance, and a simple manufacturing process and excellent moldability. It is intended to provide a phosphorescent fluorescent glass ceramics which can be easily produced not only in rich and opaque but also in transparent.

【０００６】[0006]

【課題を解決するための手段】セラミックス（焼結体）
に比べてガラスセラミックスは次の五つのメリットがあ
る。(1)面倒な原料混合がいらないこと。(2)ガラス熔解
の段階で撹拌する事によって非常に均一なものが得ら
れ、物性にバラツキがないこと。(3)ガラスの特性を活
かして所望の形状に容易に作れること。(4)熱処理条件
の制御により透明なものが得られること。(5)粉体を得
る場合でも最終処理温度が低いため簡単に粉砕できるこ
と。そのため、蓄光性蛍光ガラスセラミックスを実現す
れば物性の向上や上述のようなメリットを活かした、よ
り幅広い用途の展開が期待される。[Means for Solving the Problems] Ceramics (Sintered Body)
Compared with, glass ceramics has the following five advantages. (1) No need for complicated raw material mixing. (2) A very uniform product can be obtained by stirring at the glass melting stage, and there should be no variation in physical properties. (3) It can be easily made into a desired shape by taking advantage of the characteristics of glass. (4) A transparent product should be obtained by controlling the heat treatment conditions. (5) Even when obtaining powder, the final processing temperature is low, so it can be easily crushed. Therefore, if a phosphorescent fluorescent glass ceramics is realized, it is expected to develop a wider range of applications by improving the physical properties and taking advantage of the above advantages.

【０００７】本発明者は、ＳｉＯ2とアルカリ土類金属
酸化物を基本成分とした組成に希土類元素を添加して詳
細な実験を行った結果、特定の組成においてガラスを作
製でき、しかもそのガラスを熱処理することにより、残
光性を示し、且つ残光輝度が高く、残光時間が長く残光
色が多様な蓄光性蛍光ガラスセラミックスになることを
発見した。また、その原ガラスとその他の特定の原料と
を混合し、これらを焼成することによって得られた蓄光
性蛍光ガラスセラミックスは、従来の焼結法で作製した
セラミックスからなる既存の蓄光性蛍光体に比べて残光
特性が著しく向上することを発見し、本発明をなすに至
った。The present inventor has conducted a detailed experiment by adding a rare earth element to a composition containing SiO 2 and an alkaline earth metal oxide as basic components, and as a result, can produce a glass with a specific composition and It was discovered that by heat-treating, the phosphorescent fluorescent glass ceramics exhibiting afterglow, high afterglow brightness, long afterglow time and various afterglow colors. The raw glass and other specific raw materials are mixed, and the phosphorescent fluorescent glass ceramics obtained by firing these are the existing phosphorescent phosphors made of ceramics produced by a conventional sintering method. It was discovered that the afterglow characteristics were significantly improved, and the present invention was completed.

【０００８】すなわち、請求項１に記載の発明は、モル
％で ＳｉＯ2 ３０〜７０％ ＧｅＯ2 ０〜１０％ ＭｇＯ ５〜４０％ ＭＯ １０〜５５％ 但し、ＭはＣａ，Ｓｒ，Ｂａの中から選ばれる１種また
は２種以上の元素 Ｂ2Ｏ3 ０〜１５％ Ｙ2Ｏ3 ０〜１０％ Ｓｃ2Ｏ3 ０〜１０％ Ａｌ2Ｏ3 ０〜１０％ Ｇａ2Ｏ3 ０〜１５％ ＭｅＯ ０〜１０％ 但し、ＭｅはＢｅ，Ｚｎ，Ｃｄ，Ｐｂの中から選ばれる
１種または２種以上の元素 Ｒ2Ｏ ０〜６％ 但し、ＲはＬｉ，Ｎａ，Ｋの中から選ばれる１種または
２種以上の元素 Ｃｌ＋Ｆ ０〜８％ Ｂｉ2Ｏ3 ０〜８％ Ｐ2Ｏ5＋ＺｒＯ2＋ＳｎＯ2 ０〜６％ Ｓｂ2Ｏ3＋Ａｓ2Ｏ3 ０〜４％ 賦活剤として、 Ｅｕ2Ｏ3 ０.０００１〜５％（外割） 助賦活剤として、 Ｌｎ2Ｏ3 ０.０００１〜６％（外割） 但し、ＬｎはＣｅ，Ｐｒ，Ｎｄ，Ｓｍ，Ｇｄ，Ｔｂ，Ｄ
ｙ，Ｈｏ，Ｅｒ，Ｔｍ，Ｙｂ，Ｌｕの中から選ばれる１
種または２種以上の元素の組成を含有することを特徴と
する蓄光性蛍光ガラスセラミックスである。That is, the invention described in claim 1 is, in mol%, SiO 2 30 to 70% GeO 2 0 to 10% MgO 5 to 40% MO 10 to 55%, where M is Ca, Sr, or Ba. one or more elements B 2 O 3 0~15% Y 2 O 3 0~10% Sc 2 O 3 0~10% Al 2 O 3 0~10% Ga 2 O 3 0~15 selected from % MeO 0 to 10% where Me is one or more elements selected from Be, Zn, Cd and Pb R 2 O 0 to 6% where R is selected from Li, Na and K 1 or 2 or more elements of Cl + F 0 to 8% Bi 2 O 3 0 to 8% P 2 O 5 + ZrO 2 + SnO 2 0 to 6% Sb 2 O 3 + As 2 O 3 0 to 4% As an activator, Eu 2 O 3 0.0001 to 5% (outer percent) As a coactivator, Ln 2 O 3 0.0001 to 6% (outer percent) ) However, Ln is Ce, Pr, Nd, Sm, Gd, Tb, D
1 selected from y, Ho, Er, Tm, Yb, Lu
It is a phosphorescent fluorescent glass ceramics characterized by containing a composition of one kind or two or more kinds of elements.

【０００９】また、請求項２に記載の発明は、モル％で Ｂ2Ｏ3 ０.００５〜１０％ を含有することを特徴とする請求項１記載の蓄光性蛍光
ガラスセラミックスであり、請求項３に記載の発明は、
モル％で Ｙ2Ｏ3 ０.００５〜６％ を含有することを特徴とする請求項１又は２記載の蓄光
性蛍光ガラスセラミックスであり、請求項４に記載の発
明は、モル％で Ａｌ2Ｏ3 ０.００５〜６％ を含有することを特徴とする請求項１から３のうちいず
れか一項記載の蓄光性蛍光ガラスセラミックスであり、
請求項５に記載の発明は、モル％で Ｐ2Ｏ5＋ＺｒＯ2＋ＳｎＯ2 ０.００５〜５％ を含有することを特徴とする請求項１から４のうちいず
れか一項記載の蓄光性蛍光ガラスセラミックスである。The invention according to claim 2 is the phosphorescent fluorescent glass-ceramic according to claim 1, characterized in that it contains 0.005 to 10% of B 2 O 3 in mol%. The invention described in 3 is
A phosphorescent glass-ceramics according to claim 1 or 2, characterized in that it contains a Y 2 O 3 from .005 to 6% by mole%, the invention of claim 4, Al 2 in mol% O 3 is phosphorescent glass-ceramics as claimed in any one of claims 1, wherein the 3 in that it contains 0.005 to 6%,
The invention according to claim 5 contains P 2 O 5 + ZrO 2 + SnO 2 0.005 to 5% in mol%, wherein the phosphorescent fluorescent light according to any one of claims 1 to 4 is contained. It is a glass ceramics.

【００１０】また、請求項６に記載の発明は、主結晶相
としてＭ2ＭｇＳｉ2Ｏ7（但し、ＭはＣａ，Ｓｒ，Ｂａ
の中から選ばれる１種または２種以上の元素）を含有す
る請求項１から５のうちいずれか一項記載の蓄光性蛍光
ガラスセラミックスであり、請求項７に記載の発明は、
請求項１記載の組成を含有する原ガラスを熱処理して得
られることを特徴とする、請求項１から６のうちいずれ
か一項記載の蓄光性蛍光ガラスセラミックスであり、請
求項８に記載の発明は、請求項１記載の組成を含有する
原ガラスと、ＳｉＯ2，ＺｒＯ2，Ｂ2Ｏ3，Ａｌ2Ｏ3，Ｙ
2Ｏ3，ＢａＯ，ＳｒＯ，ＣａＯ，ＭｇＯ，Ｅｕ2Ｏ3，Ｎ
ｄ2Ｏ3，Ｄｙ2Ｏ3，Ｈｏ2Ｏ3，Ｔｍ2Ｏ3及びこれらに変
わる物質群から選ばれる１種または２種以上を混合し、
これらを焼成して得られることを特徴とする蓄光性蛍光
ガラスセラミックスである。In the invention according to claim 6, the main crystalline phase is M 2 MgSi 2 O 7 (where M is Ca, Sr, Ba).
The phosphorescent fluorescent glass ceramics according to any one of claims 1 to 5 containing one or more elements selected from among the above, and the invention according to claim 7,
It is obtained by heat-treating the raw glass containing the composition of Claim 1, The phosphorescent fluorescent glass ceramics of any one of Claim 1 to 6, It is characterized by the above-mentioned. The invention relates to a raw glass containing the composition according to claim 1, SiO 2 , ZrO 2 , B 2 O 3 , Al 2 O 3 and Y.
2 O 3 , BaO, SrO, CaO, MgO, Eu 2 O 3 , N
d 2 O 3, Dy 2 O 3, Ho 2 O 3, Tm 2 O 3 and a mixture of one or more members selected from group change to,
It is a phosphorescent fluorescent glass ceramics obtained by firing these.

【００１１】本発明の請求項１から５までに記載のガラ
スセラミックスの組成、および、請求項７および８にお
ける原ガラスの組成は、酸化物基準のモル％で表示した
ものである。そのガラスセラミックスの組成を上記のよ
うに限定した理由について、以下に述べる。The composition of the glass-ceramics according to claims 1 to 5 of the present invention and the composition of the raw glass according to claims 7 and 8 are expressed in mol% based on the oxide. The reason for limiting the composition of the glass ceramics as described above will be described below.

【００１２】ＳｉＯ2はガラス形成に必須の成分であ
り、またホスト結晶相の構成成分でもある。その量が３
０モル％未満では原ガラスが不安定になり、また７０モ
ル％を超えると原ガラスの溶融が困難になる。より好ま
しくは３２〜６５モル％、特に好ましくは３２〜６０モ
ル％の範囲である。SiO 2 is an essential component for glass formation and also a constituent component of the host crystal phase. The amount is 3
When it is less than 0 mol%, the raw glass becomes unstable, and when it exceeds 70 mol%, it becomes difficult to melt the raw glass. The range is more preferably 32 to 65 mol%, and particularly preferably 32 to 60 mol%.

【００１３】ＧｅＯ2はＳｉＯ2と類似な働きをする成分
で、ＳｉＯ2の一部をＧｅＯ2で置換してもガラスの生成
に影響しないが、ＧｅＯ2が高価のため１０モル％以下
にすべきである。[0013] GeO 2 is a component that similar effect as SiO 2, does not affect the generation of the glass be substituted a part of the SiO 2 in GeO 2, to 10 mol% or less for GeO 2 is expensive Should be.

【００１４】ＭｇＯはガラスの融点を下げる効果があ
り、さらにホスト結晶相を構成し、本発明の目的である
蓄光性をもたらすのに不可欠な成分である。良好な残光
特性を得るためにＭｇＯを５〜４０モル％含まなければ
ならない。より良好な前記特性を得ようとするならば、
１２〜３５モル％の範囲が好ましい。MgO has the effect of lowering the melting point of glass, and constitutes the host crystal phase, and is an essential component for providing the light-storing property which is the object of the present invention. In order to obtain good afterglow characteristics, MgO should be contained in an amount of 5 to 40 mol%. In order to obtain better said characteristics,
The range of 12-35 mol% is preferable.

【００１５】ＣａＯ，ＳｒＯ，ＢａＯはガラスの融点を
下げる効果があり、さらにＭｇＯ、ＳｉＯ2と共にホス
ト結晶相を構成するため、少なくとも1種を含まなけれ
ばならない。ガラスを得るためと良好な残光特性を得る
ために、これらの１種または２種以上の成分の合計を１
０〜５５モル％の範囲にしなければならない。より良好
な前記特性を得ようとするならば、１５〜５０モル％の
範囲が好ましい。CaO, SrO, and BaO have the effect of lowering the melting point of glass, and form a host crystal phase together with MgO and SiO 2. Therefore, at least one of them must be contained. In order to obtain glass and good afterglow characteristics, the total of one or more of these components is 1
It should be in the range of 0 to 55 mol%. In order to obtain the better characteristics, the range of 15 to 50 mol% is preferable.

【００１６】Ｂ2Ｏ3はガラスの融点を下げ、ガラスの安
定性と溶融性を改善する効果を有すると共にガラス化範
囲の拡大に大きく寄与するので１５モル％まで添加し得
るが、その以上を超えると残光特性が低下してしまう。
好ましい添加量は０.００５〜１０モル％の範囲であ
る。B 2 O 3 has the effect of lowering the melting point of glass, improving the stability and melting property of glass, and greatly contributes to the expansion of the vitrification range. Therefore, B 2 O 3 can be added up to 15 mol%, but more than that. If it exceeds, the afterglow characteristics will deteriorate.
The preferable addition amount is in the range of 0.005 to 10 mol%.

【００１７】Ｙ2Ｏ3、Ｓｃ2Ｏ3およびＡｌ2Ｏ3成分は、
ガラスの安定性と溶融性を改善する効果を有し、さらに
熱処理により析出したアルカリ土類金属シリケート結晶
相に固溶し、残光特性の向上に寄与するのでそれぞれ１
０モル％まで添加し得るが、その以上を超えるとガラス
の安定性および残光輝度は低下してしまう。好ましい添
加量は０.００５〜６モル％の範囲である。The Y 2 O 3 , Sc 2 O 3 and Al 2 O 3 components are
It has the effect of improving the stability and meltability of glass, and further forms a solid solution in the alkaline earth metal silicate crystal phase precipitated by heat treatment, contributing to the improvement of afterglow characteristics.
Although it can be added up to 0 mol%, the stability and afterglow brightness of the glass decrease if the content exceeds the above range. The preferred amount added is in the range of 0.005 to 6 mol%.

【００１８】Ｇａ2Ｏ3成分は、Ｙ2Ｏ3、Ｓｃ2Ｏ3または
Ａｌ2Ｏ3と同様にガラスの安定性と溶融性を改善する効
果を有し、さらに熱処理により析出したアルカリ土類金
属シリケート結晶相に固溶し、残光特性の向上と発光色
の多様化に寄与するので１５モル％まで添加し得るが、
その以上を超えるとガラスの安定性および残光輝度は低
下してしまう。好ましい添加量は０.００５〜１０モル
％の範囲である。The Ga 2 O 3 component has the effect of improving the stability and meltability of the glass, like Y 2 O 3 , Sc 2 O 3 or Al 2 O 3, and also has the effect of increasing the alkaline earth content deposited by heat treatment. It can be added up to 15 mol% because it forms a solid solution in the metal silicate crystal phase and contributes to improvement of afterglow characteristics and diversification of emission color.
If it exceeds the above range, the stability and afterglow brightness of the glass will decrease. The preferable addition amount is in the range of 0.005 to 10 mol%.

【００１９】二価金属酸化物（ＢｅＯ，ＺｎＯ，Ｃｄ
Ｏ，ＰｂＯ）及びアルカリ酸化物（Ｌｉ2Ｏ，Ｎａ2Ｏ，
Ｋ2Ｏ）はガラスの融点を下げ、ガラス溶融性を改善す
る効果があるので、二価金属酸化物の１種または２種以
上を合計で１０モル％まで、アルカリ酸化物の１種また
は２種以上を合計で６モル％までそれぞれ添加し得る。Divalent metal oxides (BeO, ZnO, Cd
O, PbO) and alkali oxides (Li 2 O, Na 2 O,
K 2 O) has the effect of lowering the melting point of glass and improving the glass meltability, and therefore, one or more divalent metal oxides up to 10 mol% in total, and one or two alkali oxides. It is possible to add up to 6 mol% of each of the above species.

【００２０】ハロゲン化物およびＢｉ2Ｏ3はガラスの融
点を下げ、ガラス溶融性を改善する効果があると同時に
ガラスセラミックスの残光特性の改善にも効果があるの
でそれぞれ８モル％まで添加し得るが、それ以上を添加
するとガラスの安定性と耐久性及びガラスセラミックス
の残光特性が悪くなる。Halide and Bi 2 O 3 have the effects of lowering the melting point of the glass and improving the glass meltability, and at the same time improving the afterglow characteristics of the glass ceramics, so that they can be added up to 8 mol% each. However, if more than that is added, the stability and durability of glass and the afterglow characteristics of glass ceramics deteriorate.

【００２１】Ｐ2Ｏ5，ＺｒＯ2，ＳｎＯ2の添加により所
望の結晶相が析出しやすくなるため、残光特性が向上す
る。特に、Ｐ2Ｏ5成分はＺｒＯ2，ＳｎＯ2と違ってガラ
ス形成酸化物であるため、ガラスの融点を下げると共に
ガラスの溶融性及び安定性の改善にも大きく寄与する。
しかし、これら成分の１種または２種合以上の合計は６
モル％以下に制限すべきであり、その量を超えると原ガ
ラスの溶融性、安定性およびガラスセラミックスの残光
特性が悪くなる。好ましい添加量は０.００５〜５モル
％の範囲である。Addition of P 2 O 5 , ZrO 2 and SnO 2 facilitates precipitation of a desired crystal phase, thus improving afterglow characteristics. In particular, since the P 2 O 5 component is a glass-forming oxide unlike ZrO 2 and SnO 2 , it contributes greatly to not only lowering the melting point of glass but also improving the meltability and stability of glass.
However, the total of one or more of these components is 6
It should be limited to not more than mol%, and if it exceeds this amount, the meltability and stability of the raw glass and the afterglow characteristics of the glass ceramics deteriorate. The preferred addition amount is in the range of 0.005 to 5 mol%.

【００２２】Ｓｂ2Ｏ3および/またはＡｓ2Ｏ3成分は、
ガラス溶融の際の清澄剤および還元剤として添加し得る
が、これらの１種または２種の合計量は４モル％以下で
十分である。The Sb 2 O 3 and / or As 2 O 3 components are
It may be added as a fining agent and a reducing agent at the time of melting the glass, but the total amount of one or two of these is preferably 4 mol% or less.

【００２３】Ｅｕ2Ｏ3は発光成分で必須である。出発原
料としてＥｕ3+の形で加えるが、本発明の目的の蓄光性
をもたらすのはＥｕ2+であるため、製造の過程で還元剤
または還元雰囲気を用いることによってＥｕ2+にしなけ
ればならない。Ｅｕ2Ｏ3の形で計量の場合に、その量が
０.０００１モル％未満では光吸収が悪く肉眼で認識で
きるほどの残光輝度が得られず、逆に５モル％を超える
と濃度消光を起こし、残光輝度が低下する。より好まし
くは０.００１〜４モル％、特に好ましくは０.００３〜
３モル％の範囲である。Eu 2 O 3 is an essential luminescent component. Although it is added in the form of Eu 3+ as a starting material, it is Eu 2+ that brings about the luminous properties of the present invention, so it must be converted into Eu 2+ by using a reducing agent or a reducing atmosphere during the manufacturing process. . When measuring in the form of Eu 2 O 3 , if the amount is less than 0.0001 mol%, the light absorption is poor and the afterglow that can be recognized by the naked eye cannot be obtained, and conversely, if it exceeds 5 mol%, the concentration quenching occurs. Cause the afterglow brightness to decrease. More preferably 0.001 to 4 mol%, and particularly preferably 0.003 to
It is in the range of 3 mol%.

【００２４】Ｌｎ2Ｏ3（Ｌｎ：Ｃｅ，Ｐｒ，Ｎｄ，Ｓ
ｍ，Ｇｄ，Ｔｂ，Ｄｙ，Ｈｏ，Ｅｒ，Ｔｍ，Ｙｂ，Ｌ
ｕ）は残光輝度と残光輝度時間の向上に顕著な効果があ
る成分であるが、その添加量はこれらの成分の１種また
は２種以上の合計で０.０００１モル％に達しないとそ
の効果が不十分で、逆に６モル％を超えると濃度消光を
起こし、残光特性にかえって悪い影響を与える。好まし
くは、０.００１〜５モル％、特に好ましくは０.０１〜
５モル％の範囲である。Ln 2 O 3 (Ln: Ce, Pr, Nd, S
m, Gd, Tb, Dy, Ho, Er, Tm, Yb, L
u) is a component that has a remarkable effect on the improvement of afterglow brightness and afterglow brightness time, but the addition amount of one or more of these components must reach 0.0001 mol% in total. The effect is insufficient, and conversely, when it exceeds 6 mol%, concentration quenching occurs, which adversely affects the afterglow characteristics. It is preferably 0.001 to 5 mol%, particularly preferably 0.01 to 5 mol%.
It is in the range of 5 mol%.

【００２５】請求項８に記載の発明のガラスセラミック
スは請求項１に記載の原ガラスとその他の特定の原料と
を混合し、これらを焼成して複合化することによって得
られる。ここで原ガラスと混合されるその他の特定の原
料としては、ＳｉＯ2，ＺｒＯ2，Ｂ2Ｏ3，Ｈ3ＢＯ3，Ａ
ｌ2Ｏ3，Ａｌ（ＯＨ）3，Ｙ2Ｏ3，ＢａＣＯ3，Ｂａ（Ｎ
Ｏ3）2，ＳｒＣＯ3，Ｓｒ（ＮＯ3）2，ＣａＣＯ3，Ｃａ
（ＯＨ）2，ＭｇＯ，Ｅｕ2Ｏ3，Ｎｄ2Ｏ3，Ｄｙ2Ｏ3，
Ｈｏ2Ｏ3，Ｔｍ2Ｏ3などが挙げられる。これらのうちＨ
3ＢＯ3，Ａｌ（ＯＨ）3，ＢａＣＯ3及びＢａ（Ｎ
Ｏ3）2，ＳｒＣＯ3及びＳｒ（ＮＯ3）2，ＣａＣＯ3及び
Ｃａ（ＯＨ）2はそれぞれＢ2Ｏ3，Ａｌ2Ｏ3，ＢａＯ，
ＳｒＯ，ＣａＯに変わる物質である。これらの成分は単
独でもしくは組み合わせで上述のガラスと複合化するこ
とによって異なる残光特性が得られると同時に残光輝度
も既存のものに比べて大幅に向上する。良好の残光特性
を得るためにガラスの含有量は重量％で最低０.５％が
必要である。The glass-ceramic of the invention described in claim 8 is obtained by mixing the raw glass described in claim 1 and other specific raw materials and firing them to form a composite. Here, other specific raw materials mixed with the raw glass include SiO 2 , ZrO 2 , B 2 O 3 , H 3 BO 3 , and A.
l 2 O 3 , Al (OH) 3 , Y 2 O 3 , BaCO 3 , Ba (N
O 3 ) 2 , SrCO 3 , Sr (NO 3 ) 2 , CaCO 3 , Ca
(OH) 2 , MgO, Eu 2 O 3 , Nd 2 O 3 , Dy 2 O 3 ,
Such as Ho 2 O 3, Tm 2 O 3 and the like. H of these
3 BO 3 , Al (OH) 3 , BaCO 3 and Ba (N
O 3 ) 2 , SrCO 3 and Sr (NO 3 ) 2 , CaCO 3 and Ca (OH) 2 are respectively B 2 O 3 , Al 2 O 3 , BaO,
It is a substance that replaces SrO and CaO. By combining these components alone or in combination with the above-mentioned glass, different afterglow characteristics can be obtained, and at the same time, the afterglow brightness is significantly improved as compared with the existing ones. The glass content must be at least 0.5% by weight in order to obtain good afterglow characteristics.

【００２６】[0026]

【発明の実施の形態】請求項１から７までに記載の発明
の蓄光性蛍光ガラスセラミックスは以下の方法により製
造することができる。すなわち、各出発原料を所定の比
に秤量し、よく混合した後、白金または石英またはアル
ミナるつぼを用いて空気中または還元剤を用いた環境ま
たは還元雰囲気で１２５０〜１６００℃で１〜１０時間
溶解する。空気中でガラスを作製する場合にその後の熱
処理は還元雰囲気で行うことが好ましい。還元雰囲気で
または還元剤を用いてガラスを作製する場合にはその後
の熱処理は不活性ガス雰囲気もしくは還元雰囲気で行え
ばよい。なお、還元剤としてガラスの組成に影響のない
カーボン粉末や、ケイ素、アルミニウム、亜鉛などの金
属粉末を添加することができる。バルク製品を得ようと
する場合、ガラス融液を金型に流し込み所定の形状に成
形しガラスを得る。その後、この原ガラスを７００〜１
２５０℃の範囲で０.５〜３６時間熱処理し、バルク状
の蓄光性蛍光ガラスセラミックスを得る。BEST MODE FOR CARRYING OUT THE INVENTION The phosphorescent fluorescent glass ceramics of the invention described in claims 1 to 7 can be manufactured by the following method. That is, each starting material is weighed in a predetermined ratio, mixed well, and then melted at 1250 to 1600 ° C. for 1 to 10 hours in air or in a reducing atmosphere using a platinum or quartz or alumina crucible in a reducing agent. To do. When glass is produced in air, the subsequent heat treatment is preferably performed in a reducing atmosphere. When glass is produced in a reducing atmosphere or using a reducing agent, the subsequent heat treatment may be performed in an inert gas atmosphere or a reducing atmosphere. As the reducing agent, carbon powder which does not affect the composition of glass or metal powder such as silicon, aluminum and zinc can be added. When a bulk product is to be obtained, the glass melt is poured into a mold and molded into a predetermined shape to obtain glass. Then, this raw glass is 700-1
Heat treatment is performed in the range of 250 ° C. for 0.5 to 36 hours to obtain a bulk phosphorescent fluorescent glass ceramics.

【００２７】一方、粉体の蓄光性蛍光ガラスセラミック
スを得ようとする場合、バルクガラス、あるいは粉砕し
やすくするために水などに投入し急冷して得た原ガラス
を粉砕して粉末とした後、熱処理して本発明の蓄光性蛍
光ガラスセラミックスガラスを得ることができる。さら
にこれを粉砕・分級して粉体の蓄光性蛍光ガラスセラミ
ックスとする事ができる。本発明の蓄光性蛍光ガラスセ
ラミックスはガラス相がある為、また熱処理温度が低い
為、既存の焼結法により作製されたセラミックスからな
る蓄光性蛍光体に比べて非常に粉砕しやすい。On the other hand, when it is desired to obtain powdery fluorescent fluorescent glass-ceramics, bulk glass, or raw glass obtained by rapidly cooling by pouring into water or the like for easy pulverization, is pulverized into powder. Then, the phosphorescent fluorescent glass-ceramics glass of the present invention can be obtained by heat treatment. Further, this can be crushed and classified to obtain powdery fluorescent fluorescent glass ceramics. Since the phosphorescent fluorescent glass ceramics of the present invention has a glass phase and has a low heat treatment temperature, it is much easier to grind than phosphorescent phosphors made of ceramics produced by the existing sintering method.

【００２８】さらに薄膜状の蓄光性蛍光ガラスセラミッ
クスを得ようとする場合、上述のように作製した原ガラ
ス粉末を溶媒に分散し、基板やセラミックス製品の表面
に均一に塗った後還元雰囲気で熱処理を行い、蓄光性を
有する薄膜でコーティングされた製品を得ることができ
る。When a thin film phosphorescent fluorescent glass-ceramics is to be obtained, the raw glass powder prepared as described above is dispersed in a solvent and uniformly coated on the surface of a substrate or a ceramic product and then heat-treated in a reducing atmosphere. Then, a product coated with a thin film having a luminous property can be obtained.

【００２９】また、請求項８に記載の発明の複合化ガラ
スセラミックスは次の方法により製造することができ
る。先ず、請求項１に記載の組成を含有する原ガラスを
上述の方法で作製した後、細かく粉砕する。次にこの原
ガラス粉末とその他の特定の原料をよく混合し、還元雰
囲気で９００〜１６００℃の範囲で０.５〜１２時間焼
成して蓄光性蛍光ガラスセラミックスを得る。この方法
で製造した蓄光性蛍光ガラスセラミックスは、従来の焼
結法で作製した既存の蓄光性蛍光体に比べて容易に粉砕
することができる。また、上述のように作製した原ガラ
ス粉末とその他の特定の原料とをよく混合し、金型成型
器を用いて加圧成形した後、還元雰囲気で上記の温度範
囲で焼成すれば、バルク状の蓄光性蛍光ガラスセラミッ
クスを得ることもできる。Further, the composite glass-ceramic of the invention described in claim 8 can be manufactured by the following method. First, a raw glass containing the composition according to claim 1 is produced by the above method, and then finely crushed. Next, this raw glass powder and other specific raw materials are well mixed and fired in a reducing atmosphere at 900 to 1600 ° C. for 0.5 to 12 hours to obtain a phosphorescent fluorescent glass ceramics. The phosphorescent fluorescent glass ceramics produced by this method can be easily pulverized as compared with the existing phosphorescent phosphors produced by the conventional sintering method. In addition, if the raw glass powder prepared as described above and other specific raw materials are well mixed, pressure-molded using a mold molding machine, and then fired in the above temperature range in a reducing atmosphere, it is possible to obtain a bulk material. It is also possible to obtain the phosphorescent fluorescent glass ceramics.

【００３０】[0030]

【実施例】以下、本発明を具体的な実施例により説明す
るが、本発明はこれら実施例に限定されるものではな
い。EXAMPLES The present invention will be described below with reference to specific examples, but the present invention is not limited to these examples.

【００３１】（実施例１）原料としてＳｉＯ2，Ｈ3ＢＯ
3，ＳｒＣＯ3，ＭｇＯ，Ｅｕ2Ｏ3，Ｄｙ2Ｏ3を使用す
る。これらをモル比で、ＳｉＯ2＝４３，Ｂ2Ｏ3＝２，
ＳｒＯ＝３０，ＭｇＯ＝２５，Ｅｕ2Ｏ3＝０.１，Ｄｙ2
Ｏ3＝１という組成になるように秤量し、均一に混合し
た後、１５００℃で３時間溶融した。その後、均一にな
ったガラス融液を金型に流し込み、６５０℃でアニール
した。こうして得られたガラスを更に還元雰囲気で８５
０℃で３時間熱処理を行った後、室温までに放冷し、透
明な蓄光性蛍光ガラスセラミックスを得た。(Example 1) SiO 2 , H 3 BO as raw materials
3 , SrCO 3 , MgO, Eu 2 O 3 and Dy 2 O 3 are used. The molar ratio of these is SiO 2 = 43, B 2 O 3 = 2,
SrO = 30, MgO = 25, Eu 2 O 3 = 0.1, Dy 2
The composition was weighed so that the composition was O 3 = 1 and uniformly mixed, and then melted at 1500 ° C. for 3 hours. Then, the homogenized glass melt was poured into a mold and annealed at 650 ° C. The glass thus obtained is further subjected to 85 in a reducing atmosphere.
After heat treatment at 0 ° C. for 3 hours, the mixture was allowed to cool to room temperature to obtain a transparent phosphorescent fluorescent glass ceramics.

【００３２】図１（ａ）にそのガラスセラミックスの写
真を示す。図２に本実施試料を熱処理する前後のバルク
Ｘ線回折パターンを示す。熱処理する前（ａ）はガラス
特有のブロードなカーブになっているのに対し、処理し
た後の試料（ｂ）（ガラスセラミックス）は結晶による
シャープなピークが現れている。つまり、熱処理により
ガラスから結晶質が多量に析出した。解析の結果、これ
らのピークはＳｒ2ＭｇＳｉ2Ｏ7結晶相によるものであ
ると判明した。図３に蛍光灯の照射停止後の発光スペク
トルを示す。蛍光灯の波長より短い紫外線光源などの励
起にもより、同様な発光スペクトルを示すことが確認さ
れた。図３に示すように４７０ｎｍ付近にピークを持
ち、幅広い波長範囲で発光することがわかる。尚、暗所
で青色の残光が長時間にわたって観察された。FIG. 1 (a) shows a photograph of the glass ceramic. FIG. 2 shows bulk X-ray diffraction patterns before and after the heat treatment of the sample of this example. Before the heat treatment (a) has a broad curve peculiar to glass, the sample (b) (glass ceramics) after the treatment shows a sharp peak due to the crystal. That is, a large amount of crystalline was precipitated from the glass by the heat treatment. As a result of the analysis, it was found that these peaks were due to the Sr 2 MgSi 2 O 7 crystal phase. FIG. 3 shows an emission spectrum of the fluorescent lamp after the irradiation is stopped. It was confirmed that a similar emission spectrum was exhibited by excitation with an ultraviolet light source shorter than the wavelength of a fluorescent lamp. As shown in FIG. 3, it can be seen that it has a peak near 470 nm and emits light in a wide wavelength range. A blue afterglow was observed in the dark for a long time.

【００３３】（実施例２）原料としてＳｉＯ2，Ｈ3ＢＯ
3，ＳｒＣＯ3，ＣａＣＯ3，ＭｇＯ，ＺｒＯ2，Ｅｕ
2Ｏ3，Ｄｙ2Ｏ3を使用する。これらをモル比で、ＳｉＯ
2＝４４.５，Ｂ2Ｏ3＝１，ＳｒＯ＝２３，ＣａＯ＝６，
ＭｇＯ＝２５，ＺｒＯ2＝０.５，Ｅｕ2Ｏ3＝０.０５，
Ｄｙ2Ｏ3＝１という組成になるように秤量し、均一に混
合した後、１４８０℃で３時間溶融した。その後、均一
になったガラス融液を金型に流し込み、６５０℃でアニ
ールした。こうして得られたガラスを更に還元雰囲気で
８５０℃で２時間熱処理を行った後、室温までに放冷
し、透明な蓄光性蛍光ガラスセラミックスを得た。図１
（ｂ）にそのガラスセラミックスの写真を示す。析出し
た結晶相はＸ線回折パターンの解析により（Ｓｒ1-xＣ
ａx）2ＭｇＳｉ2Ｏ7であることが分かった。図４に蛍光
灯の照射停止後の発光スペクトルを示す。４９０ｎｍ付
近にピークを持ち、幅広い波長範囲で発光することがわ
かる。尚、暗所で青緑色の残光が長時間にわたって観察
された。(Example 2) SiO 2 and H 3 BO as raw materials
3 , SrCO 3 , CaCO 3 , MgO, ZrO 2 , Eu
2 O 3 and Dy 2 O 3 are used. The molar ratio of these is SiO
2 = 44.5, B 2 O 3 = 1, SrO = 23, CaO = 6
MgO = 25, ZrO 2 = 0.5, Eu 2 O 3 = 0.05,
The composition was weighed so that the composition was Dy 2 O 3 = 1 and mixed uniformly, and then melted at 1480 ° C. for 3 hours. Then, the homogenized glass melt was poured into a mold and annealed at 650 ° C. The glass thus obtained was further heat-treated in a reducing atmosphere at 850 ° C. for 2 hours and then allowed to cool to room temperature to obtain a transparent phosphorescent fluorescent glass ceramics. Figure 1
A photograph of the glass-ceramic is shown in (b). The precipitated crystal phase was analyzed by X-ray diffraction pattern (Sr 1-x C
was found to be a x) 2 MgSi 2 O 7 . FIG. 4 shows an emission spectrum of the fluorescent lamp after the irradiation is stopped. It can be seen that it has a peak around 490 nm and emits light in a wide wavelength range. A blue-green afterglow was observed in the dark for a long time.

【００３４】（実施例３）原料としてＳｉＯ2，Ｈ3ＢＯ
3，ＳｒＣＯ3，ＣａＣＯ3，ＭｇＯ，Ｅｕ2Ｏ3，Ｄｙ2Ｏ
3を使用する。これらをモル比で、ＳｉＯ2＝４０，Ｂ2
Ｏ3＝３，ＳｒＯ＝２９，ＣａＯ＝８，ＭｇＯ＝２０，
Ｅｕ2Ｏ3＝０.０５，Ｄｙ2Ｏ3＝０.５という組成になる
ように秤量し、均一に混合した後、１５８０℃で３時間
溶融した。その後、均一になったガラス融液を水に急冷
し、ガラスを作製した。その後、ガラスを粉砕し、アル
ミナるつぼに詰めて還元雰囲気で９８０℃で５時間熱処
理を行い、本発明の蓄光性蛍光ガラスセラミックスを作
製した。さらにそのガラスセラミックスを粉砕・分級し
た試料の粉末Ｘ線回折パターンを図５に示す。析出した
結晶相は（Ｓｒ1-xＣａx）2ＭｇＳｉ2Ｏ7であることが
判明した。本ガラスセラミックスの発光ピークが４９０
ｎｍ付近にあり、暗所で青緑色の残光が長時間にわたっ
て観察された。(Example 3) SiO 2 , H 3 BO as raw materials
3 , SrCO 3 , CaCO 3 , MgO, Eu 2 O 3 , Dy 2 O
Use 3 . These are in a molar ratio of SiO 2 = 40, B 2
O 3 = 3, SrO = 29, CaO = 8, MgO = 20,
The composition was weighed so that the composition was Eu 2 O 3 = 0.05 and Dy 2 O 3 = 0.5, and the components were mixed uniformly and then melted at 1580 ° C. for 3 hours. Then, the homogenized glass melt was rapidly cooled in water to prepare glass. Then, the glass was crushed, packed in an alumina crucible, and heat-treated at 980 ° C. for 5 hours in a reducing atmosphere to produce the phosphorescent fluorescent glass ceramics of the present invention. Further, the powder X-ray diffraction pattern of the sample obtained by crushing and classifying the glass ceramics is shown in FIG. The precipitated crystal phase was found to be (Sr 1-x Ca x ) 2 MgSi 2 O 7 . The emission peak of this glass-ceramic is 490.
A blue-green afterglow in the dark was observed for a long time.

【００３５】（実施例４〜４４）実施例３と類似な方法
で、実施例４〜４４を作製し、それらの組成比と残光色
を表１にまとめた。(Examples 4 to 44) Examples 4 to 44 were prepared by a method similar to that of Example 3, and their composition ratios and afterglow colors are summarized in Table 1.

【００３６】[0036]

【表１】 [Table 1]

【００３７】[0037]

【表２】 #：蛍光灯照射停止後の発光色[Table 2] # : Emission color after fluorescent lamp irradiation is stopped

【００３８】[0038]

【表３】 #：蛍光灯照射停止後の発光色[Table 3] # : Emission color after fluorescent lamp irradiation is stopped

【００３９】表１に示すようにアルカリ土類金属酸化物
の種類と組成比を変えることによって多様な残光色が得
られる。具体的に述べるとＳｒＯをＣａＯで置き換える
と発光ピークが長波長側にシフトし、ＢａＯで置き換え
ると発光ピークが短波長側にシフトする。As shown in Table 1, various afterglow colors can be obtained by changing the type and composition ratio of the alkaline earth metal oxide. Specifically, when SrO is replaced with CaO, the emission peak shifts to the long wavelength side, and when it is replaced with BaO, the emission peak shifts to the short wavelength side.

【００４０】粉末Ｘ線回折パターンの解析により、いず
れのガラスセラミックスにおいても析出した結晶相また
は主結晶相はアルカリ土類金属シリケートであるが、ジ
ルコニウムを含んでいない組成に比べて含んだ方は残光
特性が向上したことから、ジルコニウムを含有したガラ
スセラミックスにおいてはジルコニウムもガラスから析
出し、前記の結晶相に固溶していることが推定できる。
イットリウム及びアルミニウムの場合でも同様な傾向が
認められ、さらにイットリウムあるいはアルミニウムの
添加によって発光ピークの長波長側へのシフトが見られ
た。これらの事実に基づいて、イットリウムあるいはア
ルミニウムを含有したガラスセラミックスにおいてはイ
ットリウムあるいはアルミニウムもガラスから析出し、
前記の結晶相に固溶していることが判断できる。スカン
ジウム及びガリウムについても同様なことが言える。According to the analysis of the powder X-ray diffraction pattern, the crystal phase or the main crystal phase precipitated in any of the glass ceramics was an alkaline earth metal silicate, but the one containing it remained as compared with the composition not containing zirconium. Since the optical characteristics were improved, it can be presumed that in the glass ceramic containing zirconium, zirconium was also precipitated from the glass and dissolved in the above crystal phase.
A similar tendency was observed in the case of yttrium and aluminum, and the addition of yttrium or aluminum caused a shift of the emission peak to the longer wavelength side. Based on these facts, in glass ceramics containing yttrium or aluminum, yttrium or aluminum also precipitates from the glass,
It can be determined that it is solid-dissolved in the above crystal phase. The same can be said for scandium and gallium.

【００４１】本発明の蓄光性蛍光ガラスセラミックスは
残光輝度が高く、しかも残光時間が非常に長いという特
徴がある。表２にいくつかの実施例の相対残光輝度を示
した。残光輝度の測定は試料を６００ルクスの蛍光灯で
２０分間照射した後、照射停止直後からの残光輝度を輝
度計により行った。表２の相対残光輝度は照射停止後、
４０分が経った時点で市販の蓄光性蛍光体の残光輝度を
１とした時の本発明の試料の残光輝度を表わしたもので
ある。The phosphorescent fluorescent glass ceramics of the present invention are characterized by high afterglow brightness and a very long afterglow time. Table 2 shows the relative afterglow brightness of some examples. The afterglow luminance was measured by irradiating the sample with a fluorescent lamp of 600 lux for 20 minutes, and then measuring the afterglow luminance immediately after the irradiation was stopped by a luminance meter. The relative afterglow brightness in Table 2 is
It shows the afterglow brightness of the sample of the present invention when the afterglow brightness of a commercially available phosphorescent phosphor is set to 1 after 40 minutes.

【００４２】[0042]

【表４】 [Table 4]

【００４３】表２より、本発明のガラスセラミックスの
残光輝度は市販品のよりも遥かに高いことがわかる。ま
た、暗所で肉眼で観察した結果、例えばＮｏ．10の試料
の場合は６０時間以上経っても、なお残光がはっきりと
確認された。ガラスセラミックスの場合には、組成が同
じであっても熱処理条件が違えば、物性が異なるので、
熱処理条件を最適化することによって更なる残光特性の
向上が期待される。It can be seen from Table 2 that the afterglow brightness of the glass-ceramics of the present invention is much higher than that of commercially available products. Moreover, as a result of visual observation in the dark, for example, No. In the case of 10 samples, afterglow was still clearly confirmed even after 60 hours or more. In the case of glass ceramics, even if the composition is the same, if the heat treatment conditions are different, the physical properties are different.
Further optimization of the afterglow characteristics is expected by optimizing the heat treatment conditions.

【００４４】（実施例４５）１５２０℃で３時間熔解し
た後、水に冷却して得られた組成式４５ＳｉＯ2・３０
ＳｒＯ・２０ＭｇＯ・０.０５Ｅｕ2Ｏ3・０.５Ｄｙ2Ｏ3
のガラスを４５ミクロン以下に粉砕した。この原ガラス
を２ｇ取り、さらに次の原料 ＳｉＯ2 ３.８７ｇ ＳｒＣＯ3 ９.５１ｇ ＭｇＯ １.３０ｇ Ｅｕ2Ｏ3 ０.０３ｇ Ｄｙ2Ｏ3 ０.３０ｇ と十分に混合し、アルミナるつぼに詰めて窒素９７％水
素３％の還元雰囲気で１３００℃で２時間熱処理し焼成
して青色発光の蓄光性蛍光ガラスセラミックスを得た。
析出した主結晶相はＳｒ2ＭｇＳｉ2Ｏ7であった。この
ガラスセラミックスを粉砕・分級し、蛍光灯を用いて６
００ルクスで２０分間照射した後の残光輝度を図６
（ａ）に示す。(Example 45) A compositional formula 45SiO 2 .30 obtained by melting at 1520 ° C. for 3 hours and then cooling in water
SrO ・ 20MgO ・ 0.05Eu 2 O 3・ 0.5Dy 2 O 3
Glass was ground to less than 45 microns. 2 g of this raw glass was taken, and the following raw materials SiO 2 3.87 g SrCO 3 9.51 g MgO 1.30 g Eu 2 O 3 0.03 g Dy 2 O 3 0.30 g were thoroughly mixed and packed in an alumina crucible. It was heat-treated at 1300 ° C. for 2 hours in a reducing atmosphere of nitrogen 97% and hydrogen 3% and baked to obtain a blue light-emitting phosphorescent fluorescent glass ceramics.
The precipitated main crystal phase was Sr 2 MgSi 2 O 7 . This glass-ceramic is crushed and classified, and 6
Fig. 6 shows the afterglow brightness after irradiation for 20 minutes at 00 lux.
It shows in (a).

【００４５】（実施例４６）１５００℃で３時間熔解し
た後、水に冷却して得られた組成式４５ＳｉＯ2・２２
ＳｒＯ・６ＣａＯ・２７ＭｇＯ・０.０５Ｅｕ2Ｏ3・０.
５Ｄｙ2Ｏ3のガラスを４５ミクロン以下に粉砕した。こ
の原ガラスを１.５ｇ取り、さらに、次の原料 ＳｉＯ2 ３.８７ｇ ＳｒＣＯ3 ９.５１ｇ ＭｇＯ １.３０ｇ Ｅｕ2Ｏ3 ０.０３ｇ Ｄｙ2Ｏ3 ０.３０ｇ と十分に混合し、アルミナるつぼに詰めて実施例４５と
同じ熱処理条件で熱処理し焼成して青色発光の蓄光性蛍
光ガラスセラミックスを得た。析出した主結晶相は（Ｓ
ｒ1-xＣａx）2ＭｇＳｉ2Ｏ7であった。このガラスセラ
ミックスを粉砕・分級し、蛍光灯を用いて６００ルクス
で２０分間照射した後の残光輝度を図６（ｂ）に示す。(Example 46) Composition formula 45SiO 2 · 22 obtained by melting at 1500 ° C for 3 hours and then cooling in water
SrO ・ 6CaO ・ 27MgO ・ 0.05Eu 2 O 3・ 0.
Glass of 5Dy 2 O 3 was ground to less than 45 microns. 1.5 g of this raw glass was taken, and further, the following raw materials SiO 2 3.87 g SrCO 3 9.51 g MgO 1.30 g Eu 2 O 3 0.03 g Dy 2 O 3 0.30 g were thoroughly mixed, and an alumina crucible was added. And heat-treated under the same heat-treatment conditions as in Example 45 and fired to obtain a blue-emitting phosphorescent fluorescent glass ceramics. The precipitated main crystal phase is (S
was r 1-x Ca x) 2 MgSi 2 O 7. FIG. 6B shows the afterglow brightness after crushing and classifying this glass-ceramic and irradiating it at 600 lux for 20 minutes using a fluorescent lamp.

【００４６】（比較例１） ＳｉＯ2 ３.８７ｇ ＳｒＣＯ3 ９.５１ｇ ＭｇＯ １.３０ｇ Ｅｕ2Ｏ3 ０.０３ｇ Ｄｙ2Ｏ3 ０.３０ｇ 上記の原料を十分に混合し、アルミナるつぼに詰めて窒
素９７％水素３％の還元雰囲気で１３００℃で２時間熱
処理した。こうして組成式４０ＳｉＯ2・４０ＳｒＯ・
２０ＭｇＯ・０.０５Ｅｕ2Ｏ3・０.５Ｄｙ2Ｏ3のセラミ
ックス（焼結体）からなる青色発光のアルカリ土類珪酸
塩系蓄光性蛍光体を作製した。この蓄光性蛍光体を粉砕
・分級し、蛍光灯を用いて６００ルクスで２０分間照射
した後の残光輝度を図６（ｃ）に示す。Comparative Example 1 SiO 2 3.87 g SrCO 3 9.51 g MgO 1.30 g Eu 2 O 3 0.03 g Dy 2 O 3 0.30 g The above raw materials were thoroughly mixed and packed in an alumina crucible. Heat treatment was performed at 1300 ° C. for 2 hours in a reducing atmosphere of nitrogen 97% and hydrogen 3%. In this way, the composition formula 40SiO 2 · 40SrO ·
The 20MgO · 0.05Eu 2 O 3 · 0.5Dy 2 O 3 ceramic (sintered body) alkaline earth silicate phosphorescent phosphor of blue emission comprising a was produced. The afterglow brightness after crushing and classifying this phosphorescent phosphor and irradiating it at 600 lux for 20 minutes using a fluorescent lamp is shown in FIG. 6 (c).

【００４７】図６より、原ガラスとその他の特定の原料
とを混合し、これらを焼成して得られた本発明の蓄光性
ガラスセラミックスは、組成としては極く僅かな違いに
もかかわらず、従来の焼結法で得られた、セラミックス
（焼結体）からなる蓄光性蛍光体に比べて残光特性が遙
かに優れることが明らかである。From FIG. 6, the phosphorescent glass-ceramics of the present invention obtained by mixing the raw glass and other specific raw materials and firing them are in spite of a slight difference in composition. It is clear that the afterglow characteristic is far superior to the phosphorescent phosphor made of ceramics (sintered body) obtained by the conventional sintering method.

【００４８】（実施例４７）１５００℃で３時間熔解し
た後、水に投入し急冷して得られた組成式４５ＳｉＯ2
・２２ＳｒＯ・６ＣａＯ・２７ＭｇＯ・０.１Ｅｕ2Ｏ3
・０.５Ｄｙ2Ｏ3のガラスを４５ミクロン以下に粉砕し
た。この原ガラスを１２.０ｇ取り、さらに、次の原料 Ａｌ2Ｏ3 ０.８０３ｇ ＳｒＣＯ3 １.１６２ｇ Ｅｕ2Ｏ3 ０.００５ｇ Ｄｙ2Ｏ3 ０.０２９ｇ と十分に混合し、アルミナるつぼに詰めて窒素９７％水
素３％の還元雰囲気で１１００℃で２時間熱処理し焼成
して青緑色発光の蓄光性蛍光ガラスセラミックスを得
た。このガラスセラミックスを粉砕・分級し、蛍光灯を
用いて６００ルクスで２０分間照射した後の残光輝度を
図７（ａ）に示す。(Example 47) Compositional formula 45SiO 2 obtained by melting at 1500 ° C. for 3 hours, then pouring it into water and quenching.
・ 22SrO ・ 6CaO ・ 27MgO ・ 0.1Eu 2 O 3
• 0.5 Dy 2 O 3 glass was ground to less than 45 microns. 12.0 g of this raw glass was taken, and further, the following raw materials Al 2 O 3 0.803 g SrCO 3 1.162 g Eu 2 O 3 0.005 g Dy 2 O 3 0.029 g were thoroughly mixed and packed in an alumina crucible. Then, it was heat-treated at 1100 ° C. for 2 hours in a reducing atmosphere of 97% nitrogen and 3% hydrogen and baked to obtain a phosphorescent fluorescent glass ceramic of blue-green light emission. The afterglow brightness after crushing and classifying this glass ceramics and irradiating at 600 lux for 20 minutes using a fluorescent lamp is shown in FIG.

【００４９】（実施例４８）１５００℃で３時間熔解し
た後、水に冷却して得られた組成式４５ＳｉＯ2・２２
ＳｒＯ・６ＣａＯ・２７ＭｇＯ・０.１Ｅｕ2Ｏ3・０.５
Ｄｙ2Ｏ3のガラスを４５ミクロン以下に粉砕した。この
原ガラスを１.０ｇ取り、さらに、次の原料 Ａｌ2Ｏ3 ６.０２ｇ ＳｒＣＯ3 ８.７２ｇ Ｅｕ2Ｏ3 ０.０４ｇ Ｄｙ2Ｏ3 ０.２２ｇ と十分に混合し、アルミナるつぼに詰めて窒素９７％水
素３％の還元雰囲気で１３００℃で２時間熱処理し焼成
して緑色発光の蓄光性蛍光ガラスセラミックスを得た。
このガラスセラミックスを粉砕・分級し、蛍光灯を用い
て６００ルクスで２０分間照射した後の残光輝度を図７
（ｂ）に示す。(Example 48) Compositional formula 45SiO 2 · 22 obtained by melting at 1500 ° C for 3 hours and then cooling in water
SrO ・ 6CaO ・ 27MgO ・ 0.1Eu 2 O 3・ 0.5
The glass of Dy 2 O 3 was ground to less than 45 microns. 1.0 g of this raw glass was taken, and further, the following raw materials Al 2 O 3 6.02 g SrCO 3 8.72 g Eu 2 O 3 0.04 g Dy 2 O 3 0.22 g were thoroughly mixed and packed in an alumina crucible. Then, it was heat-treated at 1300 ° C. for 2 hours in a reducing atmosphere of nitrogen 97% and hydrogen 3% and baked to obtain a green light-emitting phosphorescent fluorescent glass ceramics.
Fig. 7 shows the afterglow brightness after crushing and classifying this glass ceramics and irradiating with fluorescent lamp at 600 lux for 20 minutes.
It shows in (b).

【００５０】（比較例２） Ａｌ2Ｏ3 ６.０２ｇ ＳｒＣＯ3 ８.７２ｇ Ｅｕ2Ｏ3 ０.０４ｇ Ｄｙ2Ｏ3 ０.２２ｇ 上記の原料を十分に混合し、アルミナるつぼに詰めて窒
素９７％水素３％の還元雰囲気で１３００℃で２時間熱
処理した。こうして組成式５０Ａｌ２Ｏ３・５０ＳｒＯ
・０.１Ｅｕ2Ｏ3・０.５Ｄｙ2Ｏ3の焼結体からなる緑色
発光のアルカリ土類アルミン酸塩蓄光性蛍光体を作製し
た。この蓄光性蛍光体を粉砕・分級し、蛍光灯を用いて
６００ルクスで２０分間照射した後の残光輝度を図７
（ｃ）に示す。Comparative Example 2 Al 2 O 3 6.02 g SrCO 3 8.72 g Eu 2 O 3 0.04 g Dy 2 O 3 0.22 g The above raw materials were thoroughly mixed and filled in an alumina crucible and filled with nitrogen 97. Heat treatment was performed at 1300 ° C. for 2 hours in a reducing atmosphere of 3% by weight hydrogen. In this way, the composition formula is 50Al2O3.50SrO.
The · 0.1Eu 2 O 3 · 0.5Dy 2 O green emitting alkaline earth aluminate phosphorescent phosphor comprising a sintered body of 3 was produced. The afterglow brightness after crushing and classifying this phosphorescent phosphor and irradiating it at 600 lux for 20 minutes using a fluorescent lamp is shown in FIG.
It shows in (c).

【００５１】図７より、原ガラスとその他の特定の原料
とを混合し、これらを焼成して得られた青緑色乃至緑色
発光の本発明の蓄光性蛍光ガラスセラミックスは、従来
の焼結法で得られた、セラミックス（焼結体）からなる
比較例２の緑色発光の蓄光性蛍光体に比べて残光特性が
遙かに優れることが明らかである。From FIG. 7, the phosphorescent fluorescent glass-ceramics of the present invention of blue-green to green-light emission obtained by mixing the raw glass and other specific raw materials and firing them are produced by the conventional sintering method. It is clear that the afterglow characteristics are far superior to the obtained green light-emitting phosphorescent phosphor of Comparative Example 2 made of ceramics (sintered body).

【００５２】（実施例４９）１５２０℃で３時間溶融し
た後、水に冷却して得られた組成式４５ＳｉＯ2・３３
ＳｒＯ・２２ＭｇＯ・０.０５Ｅｕ2Ｏ3・０.５Ｄｙ2Ｏ3
のガラスを１０ミクロン以下に粉砕した。この原ガラス
粉末を８ｇ取り、２ｇのＹ2Ｏ3とよく混合してから、金
型成型器に詰めて加圧成形した。還元雰囲気で１２００
℃で５時間熱処理し焼成して青色発光のガラスセラミッ
クスを得た。蛍光灯を用いて６００ルクスで１５分間照
射した後、暗所において２４時間以上にわたって残光が
確認された。(Example 49) Compositional formula 45SiO 2 · 33 obtained by melting at 1520 ° C for 3 hours and then cooling in water
SrO ・ 22MgO ・ 0.05Eu 2 O 3・ 0.5Dy 2 O 3
Glass was ground to less than 10 microns. After taking 8 g of this raw glass powder and mixing it well with 2 g of Y 2 O 3, it was packed in a mold molding machine and pressure-molded. 1200 in a reducing atmosphere
It was heat-treated at 5 ° C. for 5 hours and baked to obtain a blue-emitting glass ceramic. After irradiating with a fluorescent lamp at 600 lux for 15 minutes, afterglow was confirmed for 24 hours or more in a dark place.

【００５３】（実施例５０）実施例４９の原ガラス粉末
を９.５ｇ取り、０.５ｇのＺｒＯ2とよく混合してか
ら、金型成型器に詰めて加圧成形し、還元雰囲気で１１
８０℃で６時間熱処理し焼成して青色発光のガラスセラ
ミックスを得た。蛍光灯を用いて６００ルクスで１５分
間照射した後、暗所において２４時間以上にわたって残
光が確認された。(Example 50) 9.5 g of the raw glass powder of Example 49 was taken, mixed well with 0.5 g of ZrO 2 and packed in a metal molder for pressure molding.
It was heat-treated at 80 ° C. for 6 hours and fired to obtain a blue-emitting glass ceramic. After irradiating with a fluorescent lamp at 600 lux for 15 minutes, afterglow was confirmed for 24 hours or more in a dark place.

【００５４】[0054]

【発明の効果】本発明は、残光輝度が高く残光時間が長
く、残光色が多様な蓄光性蛍光ガラスセラミックスを透
明なバルクから粉体まで各種の形で容易に得ることがで
きる。そしてこれらの材料は視認表示、各種標識、装飾
品、レジャー用品、建築材等、従来の蓄光性蛍光体より
も幅広い分野に利用することができる。INDUSTRIAL APPLICABILITY According to the present invention, phosphorescent fluorescent glass ceramics having high afterglow brightness, long afterglow time and various afterglow colors can be easily obtained in various forms from transparent bulk to powder. These materials can be used in a wider range of fields than conventional phosphorescent phosphors such as visual display, various signs, ornaments, leisure products, and building materials.

【図面の簡単な説明】[Brief description of drawings]

【図１】実施例１と２の蓄光性蛍光ガラスセラミックス
の外観写真である。 （ａ）：実施例１、（ｂ）：実施例２FIG. 1 is a photograph of the appearance of the phosphorescent fluorescent glass ceramics of Examples 1 and 2. (A): Example 1, (b): Example 2

【図２】実施例１のガラスを熱処理する前後のバルクＸ
線回折パターンである。 （ａ）：熱処理前（ガラス）、（ｂ）：熱処理後（ガラ
スセラミックス）2 is the bulk X before and after heat treating the glass of Example 1. FIG.
It is a line diffraction pattern. (A): Before heat treatment (glass), (b): After heat treatment (glass ceramics)

【図３】実施例１の蛍光灯照射停止後の発光スペクトル
である。FIG. 3 is an emission spectrum of Example 1 after the irradiation of the fluorescent lamp is stopped.

【図４】実施例２の蛍光灯照射停止後の発光スペクトル
である。FIG. 4 is an emission spectrum of Example 2 after the irradiation of the fluorescent lamp is stopped.

【図５】実施例３の粉末Ｘ線回折パターンである。5 is a powder X-ray diffraction pattern of Example 3. FIG.

【図６】実施例４５と４６及び比較例１の残光輝度の時
間変化である。6 is a change with time of afterglow brightness in Examples 45 and 46 and Comparative Example 1. FIG.

【図７】実施例４７と４８及び比較例２の残光輝度の時
間変化である。7 is a change with time of afterglow brightness in Examples 47 and 48 and Comparative Example 2. FIG.

───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ Ｃ０９Ｋ 11/74 ＣＰＢ Ｃ０９Ｋ 11/74 ＣＰＢ 11/75 ＣＰＢ 11/75 ＣＰＢ 11/78 ＣＰＢ 11/78 ＣＰＢ (56)参考文献 特開2000−159543（ＪＰ，Ａ) 特開 平10−167755（ＪＰ，Ａ) 特開 昭48−18473（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C03C 1/00 - 14/00 C09K 11/00 - 11/89 ＷＰＩ─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. 7 Identification code FI C09K 11/74 CPB C09K 11/74 CPB 11/75 CPB 11/75 CPB 11/78 CPB 11/78 CPB (56) References Open 2000-159543 (JP, A) JP 10-167755 (JP, A) JP 48-18473 (JP, A) (58) Fields investigated (Int.Cl. 7 , DB name) C03C 1 / 00-14/00 C09K 11/00-11/89 WPI

Claims (8)

(57)【特許請求の範囲】(57) [Claims] 【請求項１】 モル％で ＳｉＯ2 ３０〜７０％ ＧｅＯ2 ０〜１０％ ＭｇＯ ５〜４０％ ＭＯ １０〜５５％ 但し、ＭはＣａ，Ｓｒ，Ｂａの中から選ばれる１種また
は２種以上の元素 Ｂ2Ｏ3 ０〜１５％ Ｙ2Ｏ3 ０〜１０％ Ｓｃ2Ｏ3 ０〜１０％ Ａｌ2Ｏ3 ０〜１０％ Ｇａ2Ｏ3 ０〜１５％ ＭｅＯ ０〜１０％ 但し、ＭｅはＢｅ，Ｚｎ，Ｃｄ，Ｐｂの中から選ばれる
１種または２種以上の元素 Ｒ2Ｏ ０〜６％ 但し、ＲはＬｉ，Ｎａ，Ｋの中から選ばれる１種または
２種以上の元素 Ｃｌ＋Ｆ ０〜８％ Ｂｉ2Ｏ3 ０〜８％ Ｐ2Ｏ5＋ＺｒＯ2＋ＳｎＯ2 ０〜６％ Ｓｂ2Ｏ3＋Ａｓ2Ｏ3 ０〜４％ 賦活剤として、 Ｅｕ2Ｏ3 ０.０００１〜５％（外割） 助賦活剤として、 Ｌｎ2Ｏ3 ０.０００１〜６％（外割） 但し、ＬｎはＣｅ，Ｐｒ，Ｎｄ，Ｓｍ，Ｇｄ，Ｔｂ，Ｄ
ｙ，Ｈｏ，Ｅｒ，Ｔｍ，Ｙｂ，Ｌｕの中から選ばれる１
種または２種以上の元素の組成を含有することを特徴と
する蓄光性蛍光ガラスセラミックス。1. In mol% SiO 2 30 to 70% GeO 2 0 to 10% MgO 5 to 40% MO 10 to 55%, where M is one or more selected from Ca, Sr and Ba. Element B 2 O 3 0 to 15% Y 2 O 3 0 to 10% Sc 2 O 3 0 to 10% Al 2 O 3 0 to 10% Ga 2 O 3 0 to 15% MeO 0 to 10% However, Me Is one or more elements selected from Be, Zn, Cd and Pb R 2 O 0 to 6%, where R is one or more elements selected from Li, Na and K Cl + F 0-8% Bi 2 O 3 0-8% P 2 O 5 + ZrO 2 + SnO 2 0-6% Sb 2 O 3 + As 2 O 3 0-4% Eu 2 O 3 0.0001-5 as an activator percent (outer percentage) co-activator, Ln 2 O 3 0.0001~6% (outer percentage) However, Ln is Ce, Pr, Nd, m, Gd, Tb, D
1 selected from y, Ho, Er, Tm, Yb, Lu
A phosphorescent fluorescent glass ceramics characterized by containing a composition of one kind or two or more kinds of elements. 【請求項２】 モル％で Ｂ2Ｏ3 ０.００５〜１０％ を含有することを特徴とする請求項１記載の蓄光性蛍光
ガラスセラミックス。2. The phosphorescent fluorescent glass ceramic according to claim 1, which contains B 2 O 3 0.005 to 10% in mol%. 【請求項３】 モル％で Ｙ2Ｏ3 ０.００５〜６％ を含有することを特徴とする請求項１又は２記載の蓄光
性蛍光ガラスセラミックス。3. The phosphorescent fluorescent glass ceramics according to claim 1, which contains Y 2 O 3 0.005 to 6% in mol%. 【請求項４】 モル％で Ａｌ2Ｏ3 ０.００５〜６％ を含有することを特徴とする請求項１から３のうちいず
れか一項記載の蓄光性蛍光ガラスセラミックス。4. The phosphorescent fluorescent glass-ceramic according to claim 1, which contains Al 2 O 3 0.005 to 6% in mol%. 【請求項５】 モル％で Ｐ2Ｏ5＋ＺｒＯ2＋ＳｎＯ2 ０.００５〜５％ を含有することを特徴とする請求項１から４のうちいず
れか一項記載の蓄光性蛍光ガラスセラミックス。5. The phosphorescent fluorescent glass ceramics according to claim 1, which contains P 2 O 5 + ZrO 2 + SnO 2 0.005 to 5% in mol%. 【請求項６】 主結晶相としてＭ2ＭｇＳｉ2Ｏ7（但
し、ＭはＣａ，Ｓｒ，Ｂａの中から選ばれる１種または
２種以上の元素）を含有する請求項１から５のうちいず
れか一項記載の蓄光性蛍光ガラスセラミックス。6. The method according to claim 1, wherein M 2 MgSi 2 O 7 (where M is one or more elements selected from Ca, Sr and Ba) is contained as a main crystal phase. The phosphorescent fluorescent glass ceramic according to the item 1. 【請求項７】 請求項１記載の組成を含有する原ガラス
を熱処理して得られることを特徴とする、請求項１から
６のうちいずれか一項記載の蓄光性蛍光ガラスセラミッ
クス。7. The phosphorescent fluorescent glass-ceramic according to claim 1, which is obtained by heat-treating a raw glass containing the composition according to claim 1. 【請求項８】 請求項１記載の組成を含有する原ガラス
と、ＳｉＯ2，ＺｒＯ2，Ｂ2Ｏ3，Ａｌ2Ｏ3，Ｙ2Ｏ3，Ｂ
ａＯ，ＳｒＯ，ＣａＯ，ＭｇＯ，Ｅｕ2Ｏ3，Ｎｄ2Ｏ3，
Ｄｙ2Ｏ3，Ｈｏ2Ｏ3，Ｔｍ2Ｏ3およびこれらに変わる物
質群から選ばれる１種または２種以上を混合し、これら
を焼成して得られることを特徴とする蓄光性蛍光ガラス
セラミックス。8. A raw glass containing the composition according to claim 1, and SiO 2 , ZrO 2 , B 2 O 3 , Al 2 O 3 , Y 2 O 3 and B.
aO, SrO, CaO, MgO, Eu 2 O 3 , Nd 2 O 3 ,
Dy 2 O 3, Ho 2 O 3, Tm 2 O 3 and a mixture of one or more members selected from these changes substance groups, phosphorescent glass-ceramics, characterized in that it is obtained by firing these .
JP11274299A 1998-09-22 1999-04-20 Luminescent fluorescent glass ceramics Expired - Fee Related JP3396443B2 (en)

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US09/398,593 US6287993B1 (en) 1998-09-22 1999-09-17 Long-lasting phosphorescent glasses and glass-ceramics

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JP26813798 1998-09-22
JP10-268137 1998-09-22
JP1981899 1999-01-28
JP11-19818 1999-01-28
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