JPS58173182A - Light-storing glaze and light-storing fluorescent pottery product - Google Patents
Light-storing glaze and light-storing fluorescent pottery productInfo
- Publication number
- JPS58173182A JPS58173182A JP5685582A JP5685582A JPS58173182A JP S58173182 A JPS58173182 A JP S58173182A JP 5685582 A JP5685582 A JP 5685582A JP 5685582 A JP5685582 A JP 5685582A JP S58173182 A JPS58173182 A JP S58173182A
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- Japan
- Prior art keywords
- weight
- parts
- light
- glaze
- storing
- 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.)
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Links
Abstract
Description
【発明の詳細な説明】
本発明は、蓄光螢光性若しくは蓄光発光性陶磁製品及び
該陶磁製品の釉面形成に使用される釉薬に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a phosphorescent or luminescent ceramic product and a glaze used for forming the glaze surface of the ceramic product.
蓄光螢光体とは、主として可視光線、紫外線等の放射エ
ネルｆ−を蓄え、これを暗所で徐々に解放して螢光或い
は発光現象を示す物質をいい、種々の物質がこの現象を
呈することが知られている。A phosphorescent material is a substance that stores radiant energy f-, mainly visible light and ultraviolet rays, and gradually releases it in the dark to exhibit a fluorescent or luminescent phenomenon.A variety of substances exhibit this phenomenon. It is known.
これ等のうちで本、発光性に優れ且つ残光性も長い等の
理由により、ＺｎＳ 、 ＣｄＳ等の硫化物系蓄光螢光
体が主として使用されている。これ等硫化物系蓄光螢光
体は、通常塩化ビニル樹脂等のづラス予ツク材料中に混
和され、成形された状態歳いはプラスチック成形体に塗
布された状態で使用され、暗所における或いは夜間の標
識、装飾、照明等に利用されているが、耐候性、耐熱性
、耐摩耗性等が充分で表い。又、螢光ホウＯつや螢光性
人造石材等において、蓄光螢光体を使用した例も存在す
るが、陶磁器に施して７４０℃以上の高温で焼成すると
硫化物が酸化分解して、螢光性が大巾に失われるので、
やはり満足すべき本のとはいい難い。Among these, sulfide-based luminescent phosphors such as ZnS and CdS are mainly used because of their excellent luminescence and long afterglow properties. These sulfide-based luminescent phosphors are usually mixed into glass preparatory materials such as vinyl chloride resin and used in a molded state or coated on a plastic molded body, and are used in dark places or It is used for nighttime signs, decorations, lighting, etc., and is known for its weather resistance, heat resistance, and abrasion resistance. In addition, there are examples of using phosphorescent materials in fluorescent porcelain and fluorescent artificial stone materials, but when applied to ceramics and fired at high temperatures of 740°C or higher, the sulfides are oxidized and decomposed, causing the fluorescent material to emit light. Because sexuality is completely lost,
After all, it's hard to say that it's a satisfying book.
本発明者は、上記の如き現状に鑑みて、セラミック製品
に蓄光螢光性を与えるべく種々研究を重ねた結果、硫化
物系蓄光螢光体を含む特定組成のフリットを使用して陶
磁製品を製造する場合に１土、７４０℃以上の高温での
焼成に際しても硫化物系蓄光螢光体の保護層が形成され
、従って最終的に得られる陶磁器製品は、本来の優れた
耐候性、耐熱性、耐摩耗性等に加えて、優れた発光性及
び残光性をも発揮することを見出した。即ち、本発明は
、■Ｂ２０３１０〜５０重量部、Ａｔ２０３１〜２０重
量部、ＺｒＬｏ ０ ” １０重量部、Ｎα２０２〜１
５重量部、５Ｌ０２０〜６０重量部、Ｃｅｔｏ ０−１
５重量部、Ｋ２Ｏ０〜５重量部及びＫ９Ｏ０〜５重量部
の合計１００重量に硫化物系蓄光螢光体５〜６０重量部
を加えた蓄光性釉薬、及び■Ｂ２０３１０〜５０重量部
、Ａｔ２０３１〜２０重量部、ＺＦ＆００ ” １０重
量部、Ｎａ２Ｏ２〜１５重量部、５ｔＯ２０〜６０重量
部、ＣａＯＱ〜１５重量部、Ｘ、、ＯＯ〜５重量部及び
Ｍ９００〜５重量部の合計１００重量部と硫化物系蓄光
螢光体５〜６０重量部とからなる釉薬により形成された
釉面を備え九蓄光螢光性陶磁器製品を提供くと本以下の
如き要件が要求される。In view of the above-mentioned current situation, the inventor of the present invention has conducted a variety of researches to impart phosphorescent properties to ceramic products, and as a result, the present inventor has developed ceramic products using a frit of a specific composition containing a sulfide-based phosphorescent material. During manufacturing, a protective layer of sulfide-based luminescent phosphor is formed even when fired at high temperatures of 740°C or higher, so the final ceramic product has excellent weather resistance and heat resistance. It has been found that in addition to abrasion resistance, it also exhibits excellent luminescence and afterglow properties. That is, in the present invention, (1) B20310-50 parts by weight, At2031-20 parts by weight, ZrLo 0'' 10 parts by weight, Nα202-1
5 parts by weight, 5L020-60 parts by weight, Ceto 0-1
5 parts by weight, 0 to 5 parts by weight of K2O, and 0 to 5 parts by weight of K9O, a total of 100 parts by weight, and 5 to 60 parts by weight of a sulfide-based luminescent phosphor, and ■B20310 to 50 parts by weight, At2031 to 20 Parts by weight, 10 parts by weight of ZF&00'', 15 parts by weight of Na2O2, 20-60 parts by weight of 5tO, 15 parts by weight of CaOQ, 5 parts by weight of X, OO, and 5 parts by weight of M900 in total, and sulfide-based When providing a phosphorescent ceramic product having a glaze surface formed with a glaze containing 5 to 60 parts by weight of phosphorescent material, the following requirements are required.
イ 硫化物系蓄光螢光体と反応して有色硫化物を形成す
る成分を含まないこと。(a) It must not contain components that react with sulfide-based luminescent phosphors to form colored sulfides.
（２）釉面形成の為の焼成に際し、硫化物系螢光体の酸
化分解以下の温度でガラス質の螢光体保護層が形成され
ること。(2) During firing to form a glaze surface, a glassy phosphor protective layer is formed at a temperature below the oxidative decomposition of the sulfide phosphor.
Ｑ〜 焼成時の高温において螢光体を封じ込めて安定化
させ、螢光体結晶の破壊及び分解を防止し得ること。Q~ The ability to confine and stabilize the phosphor at high temperatures during firing, and prevent destruction and decomposition of the phosphor crystal.
に）陶器及び磁器上で焼成され、釉面を形成する状態で
、優れた耐候性、耐熱性、耐摩耗性等を発揮すること。2) When fired on earthenware or porcelain to form a glazed surface, it exhibits excellent weather resistance, heat resistance, abrasion resistance, etc.
（ホ）硫化物系蓄光螢光体の有する優れた発光性及び残
光性がそのｔま発揮されること。(e) The excellent luminescence and afterglow properties of the sulfide-based luminescent phosphor are fully exhibited.
本発明のフリットは、これ等の要件を全て満足するもの
である。そして、これ等の要件を充足させる為には、フ
リット１００重量部中の各成分含量を以下の如く、制御
する必要がある。The frit of the present invention satisfies all of these requirements. In order to satisfy these requirements, it is necessary to control the content of each component in 100 parts by weight of the frit as follows.
（１１Ｂ２Ｏ３は１０−５０重量部とする。Ｂ２ｏ３カ
１０重量部未満の場合には、融点が高くなり、ＺｎＳ螢
光体の保護層の形成が遅れ、残光性が失われる。一方５
０重量部を超える場合には、水への溶解性が大きくなり
、耐候性が小さくなる。(11B2O3 should be 10-50 parts by weight. If B2O3 is less than 10 parts by weight, the melting point will be high, the formation of the protective layer of the ZnS phosphor will be delayed, and the afterglow property will be lost. On the other hand, 5
If it exceeds 0 parts by weight, the solubility in water will increase and the weather resistance will decrease.
（ｌｉ）Ａｔ２０３は１〜２０重量部とする。Ａｔ２０
３力１重量部未満の場合には、水に対する溶解性が大き
くなり、又釉の粘性が低下する九め流下する。(li) At203 is 1 to 20 parts by weight. At20
If the amount is less than 1 part by weight, the solubility in water increases and the viscosity of the glaze decreases.
一方２０重量部を超えると、融点が高くなり、ＺｎＳの
分解温度付近でガラス化し難しくなるため、結果として
ＺｔｓＳ螢光体の保護層を形成しＫ〈くなる。On the other hand, if it exceeds 20 parts by weight, the melting point becomes high and it becomes difficult to vitrify near the decomposition temperature of ZnS, resulting in the formation of a protective layer for the ZtsS phosphor.
（２）） ＺｎＯは０〜ｌＯ重量部とする。１０重量
部を上回ると、融点が高くなυ、又ＺｎＳの分解を容易
にするため、残光性、釉面等に欠点を生じる。(2)) ZnO is 0 to 10 parts by weight. If it exceeds 10 parts by weight, the melting point is high, and ZnS is easily decomposed, resulting in disadvantages in afterglow properties, glaze surface, etc.
−ψ Ｎα２０ Ｆ１２〜！５重量部とする。Ｎα２０
が２重量部未満の場合には、主成分である５ＬＯ２、Ｂ
２Ｏ３を所定の温度で媒溶することは困難となり、陶磁
器素地上に融着することは出来ない。−ψ Nα20 F12~! 5 parts by weight. Nα20
is less than 2 parts by weight, the main components 5LO2, B
It becomes difficult to dissolve 2O3 at a predetermined temperature, and it is impossible to fuse it onto the ceramic base.
一方Ｎα２０が１５重量部を超える場合には、融点が極
端に下がり、ＺｎＳ螢光体との反応性の高いガラスとな
る。又、分解を容易にし、釉面に発泡現象を伴ない、平
滑な釉は得られない。又熱膨張率が高くなるため、貫入
を発生し易く、結果として耐候性が低下する。On the other hand, if Nα20 exceeds 15 parts by weight, the melting point will be extremely low, resulting in a glass that is highly reactive with the ZnS phosphor. In addition, it is easy to decompose, a foaming phenomenon occurs on the glaze surface, and a smooth glaze cannot be obtained. Furthermore, since the coefficient of thermal expansion becomes high, penetration is likely to occur, resulting in a decrease in weather resistance.
（Ｖ） ５ｉｎ２は６０重量部以下とする。ＳｉＯ２
カ６０重量部を上回る場合には、軟化温度が高くなシ、
螢光体の保護層の形成が遅れ、残光性が悪くなる。又平
滑で光沢を有する釉面が得られない。(V) 5in2 shall be 60 parts by weight or less. SiO2
If the amount exceeds 60 parts by weight, the softening temperature may not be high.
Formation of the protective layer of the phosphor is delayed, resulting in poor afterglow properties. Moreover, a smooth and glossy glazed surface cannot be obtained.
（ｙｉ） ＣｅｘＯは１５重量部以下とする。ＣｃＬ
Ｏが１５重量部を上回る場合には、軟化温度が著るしく
低下するため、ＺｎＳとの反応性の高いガラスとなり、
螢光体を分解せしめる。従って残光性が失われる。(yi) CexO shall be 15 parts by weight or less. CcL
When O exceeds 15 parts by weight, the softening temperature decreases significantly, resulting in a glass with high reactivity with ZnS,
Decomposes the phosphor. Therefore, the afterglow property is lost.
〜ｉｔ） Ｋ２ＯＦｉ５重量部以下とする。Ｋ２Ｏが
５重量部を上回る場合には、熱膨張率が著るしく増加す
るため、貫入が入り、釉の機械的強度が減少する。又軟
化点が低下するために残光性も悪くなる。~it) K2OFi should be 5 parts by weight or less. When K2O exceeds 5 parts by weight, the coefficient of thermal expansion increases significantly, resulting in penetration and a decrease in the mechanical strength of the glaze. Further, since the softening point is lowered, the afterglow property is also deteriorated.
（ｖｉｉＤ ＭｇＯは５重量部以下とする。ＭｔｔＯ
カ５重１に部を上回る場合には、釉の安定剤としての働
きが弱くなり、同時に軟化温度が高くなるため、ＺｎＳ
の分解を助長し、残光性が悪くなる。(viiD MgO shall be 5 parts by weight or less. MttO
If ZnS exceeds 5 parts by weight, the function of the glaze as a stabilizer becomes weak and at the same time the softening temperature increases.
This promotes decomposition and worsens the afterglow property.
尚、周知の如く、フリットの性能は、各成分とその使用
量とが相互に密接且つ複雑に関連して発揮されるもので
あり、上記（１）〜（Ｖｉｌ）の記載は、必ずしもこれ
等各成分の相互関連を充分に説明するものではない。As is well known, the performance of a frit is achieved through a close and complex relationship between each component and its usage amount, and the descriptions of (1) to (Vil) above do not necessarily refer to these. It does not fully explain the interrelationships of each component.
更に１本発明フリットにおいては、上記の基本蓄光螢光
体５〜６０重量部を使用する。蓄光螢光体が５重量部未
満では、発光が弱く且つ残光時間も短い。一方６０重量
部を上回る場合には、ＺｒＬＳの濃度が高くなり過ぎる
ため、フリットによって保護層を形成することは不能と
カリ、平滑な釉面は全く得られない。Furthermore, in one frit of the present invention, 5 to 60 parts by weight of the basic luminescent phosphor described above is used. If the amount of the luminescent phosphor is less than 5 parts by weight, the luminescence will be weak and the afterglow time will be short. On the other hand, if it exceeds 60 parts by weight, the concentration of ZrLS becomes too high, making it impossible to form a protective layer with a frit, and a smooth glazed surface cannot be obtained at all.
本発明の蓄光螢光性陶磁製品は、通常常法に従って次の
様にして製造される。粒度５〜３００μｍ程度の基本釉
薬成分１００重量部と粒度５ｏ〜５００μ肩程度の硫化
物系蓄光螢光体５〜６０重量部とを含む釉泥秦を陶器又
は磁器に施釉し、６５０−１１００℃程度で焼成する。The phosphorescent ceramic product of the present invention is manufactured in the following manner according to a conventional method. A glaze slurry containing 100 parts by weight of the basic glaze component with a particle size of about 5 to 300 μm and 5 to 60 parts by weight of a sulfide-based luminescent phosphor with a particle size of about 5 to 500 μm is applied to earthenware or porcelain, and heated at 650 to 1100°C. Fire to a certain degree.
釉泥漿の調製に際しては、必要に応じ水ガラス、ヂ士ス
トリシ、アうピア１ム、トラカントづム、ポリ塩化ビニ
ル、カルボ士ジメチルｔル０−ス、ベントナイト、酢酸
等の沈殿防止剤並びに解膠剤及び糊剤等の公知の添加物
を加えて本良い。When preparing the glaze slurry, suspending agents such as water glass, dichloromethane, apium, tracanthum, polyvinyl chloride, carboxydimethyl t-olose, bentonite, and acetic acid may be used as necessary. This can be done by adding known additives such as glue and sizing agents.
本発明の蓄光螢光性陶磁器製品は、長期にゎたり強い残
光性を示すので、停電時の非常誘導標識、夜間の道路標
識、装飾品、照明具、土木及び建築用部材等として極め
て有用である。The luminescent fluorescent ceramic products of the present invention exhibit strong afterglow properties over a long period of time, so they are extremely useful as emergency guidance signs during power outages, road signs at night, decorations, lighting equipment, civil engineering and construction materials, etc. It is.
実施例 ｌ
下記第１表に示す組成の基本フリット配合物７０重量部
Ｋ Ｚｎ５３０重量部を加え、更に水５５重量部を加え
て釉泥漿とした。次いで、５５Ｉ×６１の焼結粘土素地
板の片面に該釉泥檗を施釉し、空気中で４時間かけて８
００℃まで昇温した後、同温度に３０分間保持した。Example 1 70 parts by weight of a basic frit formulation having the composition shown in Table 1 below, 530 parts by weight of K Zn, and further 55 parts by weight of water were added to form a glaze slurry. Next, the glazed mud was applied to one side of a 55I x 61 sintered clay base plate, and glazed in air for 4 hours.
After raising the temperature to 00°C, it was maintained at the same temperature for 30 minutes.
各試験片の発光の程度及び残光時間は、第２表に示す通
りである。The degree of luminescence and afterglow time of each test piece are shown in Table 2.
第 １ 表
第 ２ 表
注：１）残光時間は、試験片を３秒間昼光下においた後
暗室に入れ、試験者が昼光中から暗室に入った場合に試
験片を確認し得た時間で示す。Table 1 Table 2 Notes: 1) Afterglow time is calculated by leaving the test piece in daylight for 3 seconds and then putting it in a dark room, and when the tester could see the test piece when entering the dark room from daylight. Shown in hours.
（以 上）(that's all)
Claims (1)
量部、Ｚｎ００〜ｌＯ重量部、Ｎα２０２〜１５重量部
、５ｔＯ２０〜６０重量部、ＣａＯＱ −１５重量部、
Ｋ２Ｏ０〜５重量部及びＫ９Ｏ０〜５重量部の合計１０
０重量に硫化物系蓄光螢光体５〜６０重量部を加えた蓄
光性釉薬。 ■ Ｂ２０３１０〜５０重量部、Ａｔ２０３１〜２０重
量部、ＺｎＯＯ〜＋ ０重量部、Ｎａ２Ｏ２〜＋ ５重
−綴部、５Ｌ０２０〜６０重量部、ＣａＯＱ −１５重
量部、Ｋ２Ｏ０〜５重量部及びＫ１Ｏ０〜５重量部の合
計１００重量部と硫化物系蓄光螢光体５〜６０重量部と
からなる釉薬により形成された釉面を備えた蓄光螢光性
陶磁器製品。[Claims] ■ B20310-50 parts by weight, At2031-20 parts by weight, Zn00-10 parts by weight, Nα202-15 parts by weight, 5tO20-60 parts by weight, CaOQ -15 parts by weight,
A total of 10 parts by weight of K2O0-5 parts by weight and K9O0-5 parts by weight
A phosphorescent glaze made by adding 5 to 60 parts by weight of a sulfide-based phosphorescent phosphor to 0 weight. ■ B20310~50 parts by weight, At2031~20 parts by weight, ZnOO~+0 parts by weight, Na2O2~+ 5 parts by weight, 5L020~60 parts by weight, CaOQ -15 parts by weight, K2O0~5 parts by weight, and K1O0~5 A phosphorescent ceramic product having a glaze surface formed of a glaze consisting of a total of 100 parts by weight and 5 to 60 parts by weight of a sulfide-based phosphorescent phosphor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5685582A JPS58173182A (en) | 1982-04-05 | 1982-04-05 | Light-storing glaze and light-storing fluorescent pottery product |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5685582A JPS58173182A (en) | 1982-04-05 | 1982-04-05 | Light-storing glaze and light-storing fluorescent pottery product |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS58173182A true JPS58173182A (en) | 1983-10-12 |
| JPS6238307B2 JPS6238307B2 (en) | 1987-08-17 |
Family
ID=13039021
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5685582A Granted JPS58173182A (en) | 1982-04-05 | 1982-04-05 | Light-storing glaze and light-storing fluorescent pottery product |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS58173182A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1992014799A1 (en) * | 1991-02-19 | 1992-09-03 | Hirofumi Moriyama | Luminous member and paint |
| WO1998023791A1 (en) * | 1996-11-29 | 1998-06-04 | Riedel-De Haen Aktiengesellschaft | Stratified composite with phosphorescent properties, method for the production and the use thereof |
| JP2000086329A (en) * | 1998-09-11 | 2000-03-28 | Kazuo Saito | Porcelain provided with glass and luminous agent |
| EP1746078A1 (en) * | 2005-07-20 | 2007-01-24 | Universal Light Co., Ltd. | Fired product having luminous function and evacuation route guiding sign device using fired product |
| CN113968752A (en) * | 2021-09-27 | 2022-01-25 | 蒙娜丽莎集团股份有限公司 | Anti-counterfeiting ceramic tile and preparation method thereof |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63165007U (en) * | 1987-04-15 | 1988-10-27 | ||
| JPH0361011U (en) * | 1989-10-17 | 1991-06-14 | ||
| JPH10171389A (en) * | 1996-12-10 | 1998-06-26 | Inax Corp | Light storage plate and method of using light storage plate |
| JP3789038B2 (en) * | 1998-04-02 | 2006-06-21 | 日本カーバイド工業株式会社 | Information display device |
-
1982
- 1982-04-05 JP JP5685582A patent/JPS58173182A/en active Granted
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1992014799A1 (en) * | 1991-02-19 | 1992-09-03 | Hirofumi Moriyama | Luminous member and paint |
| WO1998023791A1 (en) * | 1996-11-29 | 1998-06-04 | Riedel-De Haen Aktiengesellschaft | Stratified composite with phosphorescent properties, method for the production and the use thereof |
| US6528186B1 (en) | 1996-11-29 | 2003-03-04 | Honeywell International Inc. | Stratified composite with phosphorescent properties, method for the production and the use thereof |
| JP2000086329A (en) * | 1998-09-11 | 2000-03-28 | Kazuo Saito | Porcelain provided with glass and luminous agent |
| EP1746078A1 (en) * | 2005-07-20 | 2007-01-24 | Universal Light Co., Ltd. | Fired product having luminous function and evacuation route guiding sign device using fired product |
| CN113968752A (en) * | 2021-09-27 | 2022-01-25 | 蒙娜丽莎集团股份有限公司 | Anti-counterfeiting ceramic tile and preparation method thereof |
| CN113968752B (en) * | 2021-09-27 | 2022-11-18 | 蒙娜丽莎集团股份有限公司 | Anti-counterfeiting ceramic tile and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6238307B2 (en) | 1987-08-17 |
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