JPH0438700B2 - - Google Patents
Info
- Publication number
- JPH0438700B2 JPH0438700B2 JP8528687A JP8528687A JPH0438700B2 JP H0438700 B2 JPH0438700 B2 JP H0438700B2 JP 8528687 A JP8528687 A JP 8528687A JP 8528687 A JP8528687 A JP 8528687A JP H0438700 B2 JPH0438700 B2 JP H0438700B2
- Authority
- JP
- Japan
- Prior art keywords
- phosphor
- weight
- glaze
- present
- glass
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 34
- 239000011521 glass Substances 0.000 claims description 24
- 238000002844 melting Methods 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 14
- 230000008018 melting Effects 0.000 claims description 13
- 210000003298 dental enamel Anatomy 0.000 description 12
- 239000000919 ceramic Substances 0.000 description 8
- 239000000049 pigment Substances 0.000 description 8
- 239000011230 binding agent Substances 0.000 description 7
- 238000010304 firing Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 4
- 238000009877 rendering Methods 0.000 description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 101100496858 Mus musculus Colec12 gene Proteins 0.000 description 3
- 229910004283 SiO 4 Inorganic materials 0.000 description 3
- 238000005299 abrasion Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 229910005793 GeO 2 Inorganic materials 0.000 description 2
- -1 O 3 Substances 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 125000005396 acrylic acid ester group Chemical group 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N alpha-Methyl-n-butyl acrylate Natural products CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- 239000001055 blue pigment Substances 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 239000001056 green pigment Substances 0.000 description 2
- 238000004020 luminiscence type Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 239000001054 red pigment Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 1
- MQWCQFCZUNBTCM-UHFFFAOYSA-N 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylphenyl)sulfanyl-4-methylphenol Chemical compound CC(C)(C)C1=CC(C)=CC(SC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O MQWCQFCZUNBTCM-UHFFFAOYSA-N 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- FJWGYAHXMCUOOM-QHOUIDNNSA-N [(2s,3r,4s,5r,6r)-2-[(2r,3r,4s,5r,6s)-4,5-dinitrooxy-2-(nitrooxymethyl)-6-[(2r,3r,4s,5r,6s)-4,5,6-trinitrooxy-2-(nitrooxymethyl)oxan-3-yl]oxyoxan-3-yl]oxy-3,5-dinitrooxy-6-(nitrooxymethyl)oxan-4-yl] nitrate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O)O[C@H]1[C@@H]([C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@@H](CO[N+]([O-])=O)O1)O[N+]([O-])=O)CO[N+](=O)[O-])[C@@H]1[C@@H](CO[N+]([O-])=O)O[C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O FJWGYAHXMCUOOM-QHOUIDNNSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000010017 direct printing Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 229940116411 terpineol Drugs 0.000 description 1
- 238000010023 transfer printing Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/5022—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with vitreous materials
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Surface Treatment Of Glass (AREA)
- Glass Compositions (AREA)
Description
【発明の詳細な説明】
産業上の利用分野
本発明は、陶磁器、ガラス、ホーロー等の製品
の表面に蛍光性の絵付けを施すのに好適な釉薬に
関するものである。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a glaze suitable for applying fluorescent decoration to the surface of products such as ceramics, glass, and enamel.
従来の技術とその問題点
蛍光体とは、紫外線などの入射エネルギーによ
り励起された電子がより安定な状態へと遷移する
際にそのエネルギー差に相当するエネルギーを可
視光線として発光する物質であり、種々の物質が
この現象を呈することが知られている。この中で
も酸化物系蛍光体は酸化物であるため特に安定性
に優れている。Conventional technology and its problems A phosphor is a substance that emits visible light with energy corresponding to the energy difference when electrons excited by incident energy such as ultraviolet rays transition to a more stable state. It is known that various substances exhibit this phenomenon. Among these, oxide-based phosphors have particularly excellent stability because they are oxides.
蛍光体は紙やプラスチツク等の上に塗布或いは
印刷されたり、混練して成型したりして使用さ
れ、紫外線のみを出すブラツクランプで照射する
ことにより発光させて、デイスプレイや標識、そ
れに証券や紙幣の隠しマーク等に利用されてき
た。しかしながら、基板材料が紙やプラスチツク
等に限定されていたため耐候性、耐熱性、耐摩耗
性、それにデイスプレイとして利用した時の質感
等が十分ではなかつた。 Phosphors are used by being coated or printed on paper or plastic, or kneaded and molded, and are emitted by irradiation with a Bratz clamp that emits only ultraviolet rays, making them useful for displays, signs, securities, and banknotes. It has been used as a hidden mark. However, since the substrate material was limited to paper, plastic, etc., it did not have sufficient weather resistance, heat resistance, abrasion resistance, or texture when used as a display.
これを解決するために、蛍光体をホーロや陶磁
器にガラス粉末とともに焼成して使用した例もあ
るが、焼成時の高温で酸化、分解したり、ガラス
の成分と反応する等の為に蛍光性が著しく劣化し
たり、焼成後の耐久性の面で必ずしも十分とは言
えなかつた。 In order to solve this problem, there are examples of using phosphors in hollow ceramics and ceramics by firing them together with glass powder, but the phosphors oxidize and decompose at high temperatures during firing, or react with the components of the glass, making them fluorescent. However, the durability after firing was not necessarily sufficient.
又、デイスプレイとして利用した時などは蛍光
体自身が殆んどの場合白色若しくは淡黄色等の淡
い色を呈するため、これらの蛍光体でパターンを
印刷してもブラツクランプを照明するまでパター
ンが判別できず、しかも、蛍光体だけでは発光色
が限定されているため蛍光発光時の演色性が必ず
しも十分ではなかつた。 Also, when used as a display, the phosphor itself exhibits a pale color such as white or pale yellow in most cases, so even if patterns are printed with these phosphors, the pattern cannot be distinguished until the Bratz clamp is illuminated. Furthermore, since the color of the emitted light is limited using only the phosphor, the color rendering properties during fluorescence emission are not necessarily sufficient.
問題点を解決するための手段
本発明者は、上記従来技術の問題点に鑑みて鋭
意研究を重ねた結果、１）特定粒径の酸化物蛍光
体と鉛含有量が特定量以下である低融点ガラスと
を特定重量比で含んでいる釉薬を印刷して焼成す
る場合には、陶磁器、ガラス、ホーロー等の表面
に非常に強固な蛍光性被膜を形成できること、
２）該被膜が耐候性、耐熱性、耐摩耗性等に優れ
ていること、並びに３）該被膜が、優れた発光
性、重厚な質感及び豊富な演色性を有することを
見出し、本発明を完成した。Means for Solving the Problems As a result of extensive research in view of the problems of the above-mentioned prior art, the inventors of the present invention have found that: When printing and firing a glaze containing a specific weight ratio of melting point glass, it is possible to form a very strong fluorescent film on the surface of ceramics, glass, enamel, etc.
We discovered that 2) the film has excellent weather resistance, heat resistance, abrasion resistance, etc., and 3) that the film has excellent luminescence, a profound texture, and rich color rendering properties, and we have developed the present invention. completed.
即ち本発明は、平均粒径10.0μｍ以下の酸化物
蛍光体100重量部と鉛含有率10.0重量％以下の低
融点ガラス５〜300重量部とを含む蛍光性釉薬に
係る。 That is, the present invention relates to a fluorescent glaze containing 100 parts by weight of an oxide phosphor having an average particle size of 10.0 μm or less and 5 to 300 parts by weight of a low-melting glass having a lead content of 10.0% by weight or less.
酸化物系蛍光体としては、公知のものが何れも
使用でき、Y2O3：Eu，0.5MgF2：3.5MgO：
GeO2：Mn等の赤色系蛍光体、Zn2SiO4：Mn，
2ZrO・GeO2：Mn，ZnO：Zn等の緑色系蛍光体、
（Sr（PO4）2：SrCl2）：Eu等の青色系蛍光体等を挙
げることができる。本発明では、これら酸化物系
蛍光体の１種または２種以上を使用できる。蛍光
体の粒径は10μｍ以下とするのがよい。10μｍを
越えると、スクリーンの目詰り、蛍光面のざらつ
き等が大きくなり、印刷適性、発光効率等が低下
する。蛍光体の配合量は特に制限されないが、通
常釉薬全量の10〜80重量％程度とすればよい。本
発明では、上記蛍光体は顔料をも包含するものと
する。蛍光体とともに顔料を添加することによつ
て、ブラツクランプ非照射時の色付けと照射時の
演色性とが向上する。顔料としては公知のものが
何れも使用でき、例えば、Fe2O3，MnO−Al2
O3，Cr2O3−SnO2等の赤色系顔料、CuO，Cr2
O3，NiO2，CoO−Cr2O3等の緑色系顔料、Cr2O3
−V2O5，CoO，MnO2−P2O5等の青色系顔料等
を挙げることができる。これらの中から、螢光
体、フリツトと反応して蛍光性を劣化させること
のないものを、それぞれの条件において選び出し
て用いれば良い。顔料の配合量は、蛍光体の量を
100重量部とした場合、300重量部以下程度とすれ
ばよい。300重量部を越えると、蛍光性が低下す
る。 Any known oxide phosphor can be used, including Y 2 O 3 :Eu, 0.5MgF 2 :3.5MgO:
GeO 2 : Red phosphor such as Mn, Zn 2 SiO 4 : Mn,
2ZrO・GeO 2 :Mn, ZnO: Green phosphor such as Zn,
(Sr(PO 4 ) 2 :SrCl 2 ): Blue phosphors such as Eu and the like can be mentioned. In the present invention, one or more of these oxide-based phosphors can be used. The particle size of the phosphor is preferably 10 μm or less. If it exceeds 10 μm, clogging of the screen, roughness of the phosphor screen, etc. will increase, and printability, luminous efficiency, etc. will decrease. The amount of the phosphor to be blended is not particularly limited, but it may normally be about 10 to 80% by weight of the total amount of the glaze. In the present invention, the above-mentioned phosphor also includes a pigment. By adding a pigment together with a phosphor, coloring when not irradiated with a Bratz clamp and color rendering when irradiated are improved. Any known pigment can be used, such as Fe 2 O 3 , MnO-Al 2
Red pigments such as O 3 , Cr 2 O 3 -SnO 2 , CuO, Cr 2
Green pigments such as O 3 , NiO 2 , CoO-Cr 2 O 3 , Cr 2 O 3
Examples include blue pigments such as -V 2 O 5 , CoO, MnO 2 -P 2 O 5 . Among these, those that do not react with the phosphor or the frit and deteriorate the fluorescence may be selected and used under the respective conditions. The amount of pigment blended depends on the amount of phosphor.
When the amount is 100 parts by weight, it may be about 300 parts by weight or less. If it exceeds 300 parts by weight, fluorescence will decrease.
低融点ガラスは、酸化物系蛍光体を陶磁器、ガ
ラス、ホーロー等の基材表面に強力に接着させ
る。低融点ガラスとしては、鉛含量率が10.0重量
％以下で融点が400〜800℃程度である公知のもの
が何れも使用できる。鉛含有量が10.0重量％を越
えると、焼成時に鉛と蛍光体とが反応して発光効
率を著しく低下させる。低融点ガラスの粒径は特
に限定されないが、通常1.0〜30μｍ程度のものを
使用すればよい。低融点ガラスは、酸化物系蛍光
体の量を100重量部とした場合、５〜300重量部程
度、好ましくは10.0〜150.0重量部程度となるよ
うに配合すればよい。５重量部未満では、接着剤
としての機能が不充分となり、一方300重量部を
越えると、蛍光性が低下する。 Low melting point glass allows oxide phosphors to strongly adhere to the surface of base materials such as ceramics, glass, and enamel. As the low melting point glass, any known glass having a lead content of 10.0% by weight or less and a melting point of about 400 to 800°C can be used. If the lead content exceeds 10.0% by weight, the lead will react with the phosphor during firing, significantly reducing luminous efficiency. The particle size of the low melting point glass is not particularly limited, but it is usually about 1.0 to 30 μm. The low melting point glass may be blended in an amount of about 5 to 300 parts by weight, preferably about 10.0 to 150.0 parts by weight, when the amount of the oxide phosphor is 100 parts by weight. If it is less than 5 parts by weight, its function as an adhesive will be insufficient, while if it exceeds 300 parts by weight, the fluorescence will decrease.
本発明釉薬は、上記成分の他にバインダーを含
んでいる。バインダーとしては、通常の釉薬に含
まれているものが何れも使用でき、例えばアクリ
ル酸エステル、エチルセルロース、ニトロセルロ
ース、ポリビニルブチラールメタクリル酸ブチル
エステルなど、及びこれらの混合物等を挙げるこ
とができる。本発明では、これらのバインダーを
適当な溶剤に溶解して使用する。溶剤としては、
例えばテルピネオール、ブチルカルビトール、酢
酸エチル、酢酸アミン等、及びこれらの混合物等
を挙げることができる。上記溶液中のバインダー
量は特に制限されないが、通常10〜50重量％程度
とすればよい。バインダーの溶剤溶液の配合量は
特に制限されないが、通常バインダー量が釉薬全
量の1.0〜20重量％程度となるようにすればよい。 The glaze of the present invention contains a binder in addition to the above components. As the binder, any binder contained in ordinary glazes can be used, such as acrylic acid ester, ethyl cellulose, nitrocellulose, polyvinyl butyral methacrylic acid butyl ester, and mixtures thereof. In the present invention, these binders are used after being dissolved in a suitable solvent. As a solvent,
Examples include terpineol, butyl carbitol, ethyl acetate, amine acetate, and mixtures thereof. The amount of binder in the solution is not particularly limited, but it may be generally about 10 to 50% by weight. The blending amount of the binder solvent solution is not particularly limited, but it is sufficient that the binder amount is usually about 1.0 to 20% by weight based on the total amount of the glaze.
本発明釉薬は、上記各成分を三本ロール等の公
知の分散機で充分混練することによつて製造でき
る。 The glaze of the present invention can be produced by sufficiently kneading the above-mentioned components using a known disperser such as a three-roll mill.
本発明釉薬を使用して陶磁器、ガラス、ホーロ
ー等の基板に蛍光パターンを形成させる当つて
は、公知の方法が何れも採用できる。例えば、本
発明釉薬で基板上にパターンを形成し、次いでこ
れを500〜850℃程度で焼成すればよい。基板上に
パターンを形成させるに当つては公知の方法が何
れも採用でき、例えば、スクリーンによる直接印
刷、スライド転写紙による転写印刷、筆書き、浸
漬等を挙げることができる。 Any known method can be used to form a fluorescent pattern on a substrate such as ceramics, glass, or enamel using the glaze of the present invention. For example, a pattern may be formed on a substrate using the glaze of the present invention and then fired at about 500 to 850°C. Any known method can be used to form a pattern on the substrate, including direct printing with a screen, transfer printing with a slide transfer paper, writing with a brush, dipping, and the like.
本発明では、本発明釉薬の２種以上を混合して
所望の色を有する釉薬を調製し、これを上記方法
に準じて印刷及び焼成し、蛍光パターンを形成し
てもよい。 In the present invention, a glaze having a desired color may be prepared by mixing two or more of the glazes of the present invention, and this may be printed and fired according to the above method to form a fluorescent pattern.
発明の効果
本発明釉薬を使用すれば、陶磁器、ガラス、ホ
ーロー等の基材表面に強固な蛍光製被膜を形成で
きる。また、該被膜は、耐候性、耐熱性、耐摩耗
性等に優れ、しかも、優れた発光性、重厚な質感
及び豊富な演色性を有している。Effects of the Invention By using the glaze of the present invention, a strong fluorescent film can be formed on the surface of a substrate such as ceramics, glass, enamel, etc. Further, the coating has excellent weather resistance, heat resistance, abrasion resistance, etc., as well as excellent luminescence, deep texture, and rich color rendering properties.
実施例
以下に実施例を挙げ、本発明をより一層明瞭な
ものとする。Examples Examples will be given below to further clarify the present invention.
実施例１ ホーロー用蛍光釉薬
赤色蛍光体Y2O3：Eu（平均粒径2.0μｍ）60重量
％、赤色顔料Fe2O310重量％、下記組成を有する
低融点ガラス（平均粒径5.0μｍ）15重量％及びア
クリル酸エステルの30％タピノール溶液15重量％
を、三本ロールにて混合分散し、ペースト状の本
発明釉薬ａを得た。Example 1 Fluorescent glaze for enamel Red phosphor Y 2 O 3 : Eu (average particle size 2.0 μm) 60% by weight, red pigment Fe 2 O 3 10% by weight, low melting point glass having the following composition (average particle size 5.0 μm) ) 15% by weight and 30% tapinol solution of acrylic esters 15% by weight
were mixed and dispersed using three rolls to obtain paste-like glaze a of the present invention.
・低融点ガラス
SiO2 43％
Na2Ｏ 20％
CaO ６％
K2Ｏ 1.0％
Al2O3 1.1％
MgO 1.3％
B2O3 27.6％
PbO −
蛍光体として緑色用蛍光体Zn2SiO4：Mn（平均
粒径1.8μｍ）を、及び顔料として緑色顔料CuOを
使用する以外は、上記と同様にしてペースト状の
本発明釉薬ｂを得た。・Low melting point glass SiO 2 43% Na 2 O 20% CaO 6% K 2 O 1.0% Al 2 O 3 1.1% MgO 1.3% B 2 O 3 27.6% PbO − Green phosphor Zn 2 SiO 4 as a phosphor: A paste-like glaze b of the present invention was obtained in the same manner as described above, except that Mn (average particle size 1.8 μm) and the green pigment CuO were used as the pigment.
蛍光体として青色用蛍光体（Sr（PO4）2：
SrCl2）：Eu（平均粒径2.5μｍ）を、及び顔料とし
て青色顔料Cr2O3−V2O5を使用する以外は、上記
と同様にしてペースト状の本発明釉薬ｃを得た。 Blue phosphor (Sr( PO4 ) 2) as phosphor:
A paste-like glaze c of the present invention was obtained in the same manner as above, except that SrCl 2 ):Eu (average particle size 2.5 μm) and the blue pigment Cr 2 O 3 —V 2 O 5 were used as the pigments.
得られた本発明釉薬ａ，ｂ及びｃを適量ずつ混
合し、所望の色の釉薬を調製した。これをホーロ
ー板へスクリーンで直接印刷して乾燥し、次いで
750℃で５分焼成したところ、ホーロー板に蛍光
体が形成された。 Appropriate amounts of the obtained glazes a, b, and c of the present invention were mixed to prepare a glaze of a desired color. This is printed directly onto the enamel board using a screen, dried, and then
When fired at 750°C for 5 minutes, phosphor was formed on the enamel plate.
これを耐候性試験機（大日本プラスチツク(株)
製）アイスーパUVテスターで、63℃48時間の条
件で加速試験をしたところ、蛍光性の低下は認め
られなかつた。この耐候性試験は自然太陽光の下
では10年以上の曝露に相当するものであり十分な
耐候性を持つことが確認された。 This was tested using a weather resistance tester (Dainippon Plastics Co., Ltd.).
When an accelerated test was carried out using an I-Super UV tester (manufactured by Manufacturer Co., Ltd.) at 63°C for 48 hours, no decrease in fluorescence was observed. This weather resistance test was equivalent to over 10 years of exposure under natural sunlight, and it was confirmed that the product had sufficient weather resistance.
このホーロー板を外壁材として利用したとこ
ろ、昼間は自然光で絵柄を楽しむことができ、夜
間はブラツクランプで照明して大変素晴らしい蛍
光のデイスプレイになつた。 When we used this enamel board as an exterior wall material, we were able to enjoy the pattern in natural light during the day, and at night, when illuminated with Bratz lamps, it became a wonderful fluorescent display.
実施例２ ガラス用釉薬
赤色蛍光体Y2O3：Eu（平均粒径2.0μｍ）70重量
％、下記組成を有する低融点ガラス（平均粒径
5.0）15重量％及びアクリル酸エステルの30％タ
ピノール溶液15重量％を、三本ロールで混合分散
し、ペースト状の本発明釉薬ａを得た。Example 2 Glass glaze Red phosphor Y 2 O 3 : Eu (average particle size 2.0 μm) 70% by weight, low melting point glass having the following composition (average particle size
5.0) 15% by weight and 15% by weight of a 30% tapinol solution of acrylic acid ester were mixed and dispersed using a triple roll to obtain a paste-like glaze a of the present invention.
・低融点ガラス
Na2Ｏ 18％
CaO ７％
K2Ｏ ５％
Al2O3 ６％
P2O5 59％
ZrO2 ５％
PbO −
蛍光体として緑色用蛍光体Zn2SiO4：Mn（平均
粒径1.8μｍ）を使用する以外は、上記と同様にし
てペースト状の本発明釉薬ｂを得た。・Low melting point glass Na 2 O 18% CaO 7% K 2 O 5% Al 2 O 3 6% P 2 O 5 59% ZrO 2 5% PbO − Green phosphor Zn 2 SiO 4 :Mn (average A paste-like glaze b of the present invention was obtained in the same manner as described above, except that particles (particle size: 1.8 μm) were used.
蛍光体として青色用蛍光体（Sr（PO4）2：
SrCl2）：Eu（平均粒径2.5μｍ）を使用する以外は、
上記と同様にして本発明釉薬ｃを得た。 Blue phosphor (Sr( PO4 ) 2) as phosphor:
SrCl 2 ): Except for using Eu (average particle size 2.5 μm),
Glaze c of the present invention was obtained in the same manner as above.
得られた本発明釉薬ａ，ｂ及びｃを適量ずつ混
合し、所望の色の釉薬を調製した。これをスライ
ド転写紙の上にスクリーンで印刷して乾燥し、ガ
ラス球の上に転写して550℃で10分焼成したとこ
ろ、ガラス球の表面に蛍光体で絵柄が形成され
た。 Appropriate amounts of the obtained glazes a, b, and c of the present invention were mixed to prepare a glaze of a desired color. This was screen-printed onto slide transfer paper, dried, transferred onto a glass bulb, and fired at 550°C for 10 minutes, resulting in a phosphor pattern being formed on the surface of the glass bulb.
この球の内部に入れたブラツクランプで内側か
ら照明することにより幻想的な照明器が出来た。
しかも焼成工程を経ているため耐候性、耐熱性に
ついては従来にない大変優れた蛍光体になつた。 A fantastic illuminator was created by lighting the bulb from the inside with a Bratz clamp placed inside the bulb.
Moreover, because it has undergone a firing process, it has become a phosphor with unprecedented weather resistance and heat resistance.
実施例３ 陶磁器用釉薬
蛍光体の配合量を65重量％及び顔料の配合量を
５重量％とする以外は、実施例１と同様にして本
発明釉薬ａ，ｂ及びｃを製造した。得られた本発
明釉薬ａ，ｂ及びｃを適量ずつ混合し、所望の色
の釉薬を調製した。これを用いてスライド転写紙
の上に花柄の絵柄をスクリーンで印刷した後、図
柄の輪郭部分に金液をスクリーンで印刷して縁取
りを施し、乾燥した後白地の花瓶の上に転写し、
750℃で60分焼成した。Example 3 Glaze for ceramics Glazes a, b, and c of the present invention were produced in the same manner as in Example 1, except that the amount of phosphor was 65% by weight and the amount of pigment was 5% by weight. Appropriate amounts of the obtained glazes a, b, and c of the present invention were mixed to prepare a glaze of a desired color. After using this to screen print a floral pattern on slide transfer paper, screen print liquid gold on the outline of the pattern to create a border, and after drying, transfer it onto a white vase.
It was baked at 750°C for 60 minutes.
この様にして作成した花瓶は、通常の光のもと
では蛍光体に混入した顔料の淡い色調と金線の縁
取りで落ち着いた絵柄になり、暗所でブラツクラ
ンプを照射したときは鮮やかな蛍光色の絵柄が浮
かび上がる印象的なデイスプレイ用花瓶となつ
た。また、耐候性、耐熱性等にも優れていた。 The vase created in this way has a subdued pattern under normal light due to the pale tone of the pigment mixed with the phosphor and the gold border, but when illuminated with a Bratz clamp in the dark, it becomes a bright fluorescent image. The result is an impressive display vase with a colorful pattern. It also had excellent weather resistance and heat resistance.
実施例４ ホーロー用蛍光釉薬
下記組成を有する低融点ガラス（平均粒径5.0μ
ｍ）を使用し、ホーロー板へ印刷して焼成した後
の焼成温度を800℃とする以外は、実施例１と同
様にして、ホーロー板に蛍光体を形成した。Example 4 Fluorescent glaze for enamel Low melting point glass having the following composition (average particle size 5.0μ
A phosphor was formed on an enamel plate in the same manner as in Example 1, except that the enamel plate was printed and fired at a firing temperature of 800° C. using phosphor m).
得られた蛍光体は良好な耐候性を有し、美しい
デイスプレイになつた。 The obtained phosphor had good weather resistance and became a beautiful display.
・低融点ガラス SiO2 40.5％ NaO 11.0％ Al2O3 7.0％ B2O3 25.0％ ZnO 2.5％ K2Ｏ 5.0％ PbO 9.0％・Low melting point glass SiO 2 40.5% NaO 11.0% Al 2 O 3 7.0% B 2 O 3 25.0% ZnO 2.5% K 2 O 5.0% PbO 9.0%
Claims (1)
量部と鉛含有率10.0重量％以下の低融点ガラス５
〜300重量部とを含む蛍光性釉薬。1 100 parts by weight of an oxide phosphor with an average particle size of 10.0 μm or less and a low melting point glass with a lead content of 10.0% by weight or less 5
~300 parts by weight of a fluorescent glaze.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8528687A JPS63252939A (en) | 1987-04-07 | 1987-04-07 | Fluorescent glaze |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8528687A JPS63252939A (en) | 1987-04-07 | 1987-04-07 | Fluorescent glaze |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63252939A JPS63252939A (en) | 1988-10-20 |
| JPH0438700B2 true JPH0438700B2 (en) | 1992-06-25 |
Family
ID=13854326
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8528687A Granted JPS63252939A (en) | 1987-04-07 | 1987-04-07 | Fluorescent glaze |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63252939A (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3311254B2 (en) * | 1996-09-27 | 2002-08-05 | 伊藤忠セラテック株式会社 | Inorganic artificial ceramic granular product having luminous fluorescent properties and method for producing the same |
| JP5633114B2 (en) * | 2009-03-30 | 2014-12-03 | 日本電気硝子株式会社 | SnO-P2O5 glass used for phosphor composite material |
| JP6197445B2 (en) * | 2013-07-29 | 2017-09-20 | Toto株式会社 | Enamel article and manufacturing method thereof |
| CN106810072A (en) * | 2017-01-19 | 2017-06-09 | 万志明 | A kind of noctilucence filler and its preparation, technique for applying and use the packed art product |
| JP7823322B2 (en) * | 2021-05-31 | 2026-03-04 | Toto株式会社 | Antiviral agent containing yttrium or an yttrium compound, glaze containing said antiviral agent, and antiviral sanitary ware glazed with said glaze |
-
1987
- 1987-04-07 JP JP8528687A patent/JPS63252939A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63252939A (en) | 1988-10-20 |
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