JP2004193050A - Top plate for cooker - Google Patents

Top plate for cooker Download PDF

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Publication number
JP2004193050A
JP2004193050A JP2002362096A JP2002362096A JP2004193050A JP 2004193050 A JP2004193050 A JP 2004193050A JP 2002362096 A JP2002362096 A JP 2002362096A JP 2002362096 A JP2002362096 A JP 2002362096A JP 2004193050 A JP2004193050 A JP 2004193050A
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Japan
Prior art keywords
top plate
cooker
layer
glass
light
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JP2002362096A
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Japanese (ja)
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JP4120793B2 (en
Inventor
Narutoshi Shimatani
成俊 嶋谷
Toshimasa Kanai
敏正 金井
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Nippon Electric Glass Co Ltd
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Nippon Electric Glass Co Ltd
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Priority to JP2002362096A priority Critical patent/JP4120793B2/en
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Abstract

<P>PROBLEM TO BE SOLVED: To provide a top plate for a cooker having metallic luster and excellent recyclability and capable of being multi-colored with one kind of raw glass material. <P>SOLUTION: On a substrate 11 made of transparent glass ceramics with an average coefficient of linear thermal expansion of -5×10<SP>-7</SP>/°C at 30-500°C, a decorative layer 14 comprising a gloss layer 12 by sputtering and a light-shielding layer 13 by screen printing is formed so that it has a film material and a film thickness indicated in Tables 1-3, and the top plate 10 for the cooker of embodiments 1-10 is manufactured. <P>COPYRIGHT: (C)2004,JPO&NCIPI

Description

【0001】
【発明の属する技術分野】
本発明は、調理器用トッププレートに関するものである。
【0002】
【従来の技術】
家庭用や業務用の調理器として、従来からのガスコンロだけでなく、ラジエントヒーターやハロゲンヒーターを用いた赤外線加熱調理器、電磁加熱(IH)調理器が用いられるようになってきた。
【0003】
電磁加熱調理器に用いられるトッププレートには、熱効率、安全性、熱衝撃性の点から、電磁誘導加熱量が小さく、低熱膨張であるガラス、セラミックス、結晶化ガラス等の材料が使用されている。
【0004】
従来、トッププレートとして、琺瑯やステンレスを使用していたガス調理器においても、これらの材料の美観や清掃性が優れていることから、低熱膨張のガラス、セラミックス、結晶化ガラス等の非金属系材料が使用されるようになってきた。
【0005】
調理器用トッププレートは、加熱装置に対して、水、調味料、食品等が飛散するのを防止すること以外にも、加熱装置、配線等の調理器の内部構造を隠蔽するとともに、美観を向上させることも求められるようになってきた。
【0006】
トッププレートに非金属系材料を用いて調理器の内部構造を隠蔽するための第一の方法は、調理器用トッププレートとして、金属遷移元素を用いて濃色に着色した低膨張結晶化ガラス、例えば、ブラウン色の日本電気硝子製のGC−190やショット製のセランを用いることである。
【0007】
第二の方法は、透明な低膨張ガラスの表面に印刷法を用いて遮光膜を形成する方法である。具体的には、透明な低膨張結晶化ガラス表面に、遮光膜としてガラスと無機顔料からなる膜を設けたトッププレートが知られている(例えば、特許文献1参照。)。この遮光膜は、低膨張結晶化ガラスからなる基板よりも熱膨張係数が高いため、多孔質にすることによって、膜にクラックが発生することを抑えている。また、透明な低膨張結晶化ガラスの表面に、遮光膜として貴金属と卑金属からなるラスター彩の皮膜を設けたトッププレートも知られている(例えば、特許文献2参照。)。
【0008】
また、近年においてステンレス調の調理台や調理室が普及するにつれて、調理器トッププレートが周囲の調理台や調理室と調和するよう、金属光沢を有するものが求められており、ラスター彩の皮膜を有するトッププレートは、金属光沢を有するため、この要求をも満たすことができる。
【0009】
【特許文献1】
特開平10−273342号公報
【特許文献2】
特公平7−17409号公報
【0010】
【発明が解決しようとする課題】
しかし、第一の方法によってトッププレートの多色化を達成するには、色数や色濃度に応じて多品種のガラス生地を用意しなければならず、コストアップになるばかりか、ガラスに適した遷移金属元素も限られるため、多彩な色を出すことに限界があった。また、電磁加熱調理器のトッププレートの場合に、印加される電力量を表示するインジケータを設けようとすれば、トッププレートに穴をあける必要があり、トッププレートが欠けたりあるいは割れたりしやすくなるため好ましくない。
【0011】
また、第二の方法において、特許文献1に記載された調理器用トッププレートは、金属光沢を有さず、ステンレス調の調理台や調理室との調和を図れないだけでなく、遮光層が結晶化ガラス基板の成分と異なる成分を多量に含有しているため、この遮光層が形成されたトッププレートをガラス原料としてリサイクルした際に、結晶化ガラス基板の色調や特性を変化させる虞がある。
【0012】
また、特許文献2に記載された調理器用トッププレートは、ラスター彩によって、黒、濃紺、銅色等の濃色を出せるもののその色数が少ない。また調理器用トッププレートをガラス原料としてリサイクルした際には、ガラスが着色したり、ブツ等のガラス欠陥が発生したりするだけでなく、ブツの近傍での結晶化が促進され不均質な結晶化が起こり、部分的に変色したり、白濁したりするため、美観上及び強度上の問題を有していた。すなわち、調理器用トッププレートをガラス原料としてリサイクルした際に、調理器用トッププレートに形成された遮光膜を構成する貴金属がガラスに混入すると、貴金属がガラス中にイオン、コロイド状等となって存在するようになり、ガラスの色変化を引き起こし、場合によってはガラス中に異物として存在し、さらに、この異物を結晶核として、その異物の周囲部において異常に結晶化が進行する虞があるからである。また、遮光膜を研磨などで除去してガラス素材のみをガラス原料として再溶融すると、コストがかかるだけでなく、貴金属を含む研磨粉が発生する。この研磨粉は、貴金属を取り除いたとしても、多量の研磨剤を含むため、ガラス原料としてのリサイクルが困難となり、廃棄され環境負荷となりやすい。
【0013】
本発明の目的は、上記問題に鑑みなされたものであり、金属光沢を有し、リサイクル性に優れ、一種類のガラス生地で多色化を達成することができる調理器用トッププレートを提供することである。
【0014】
【課題を解決するための手段】
本発明の調理器用トッププレートは、透明低膨張ガラス板の表面に光沢層及び遮光層を含む装飾層が形成されてなる調理器用トッププレートであって、装飾層が実質的に貴金属元素を含まず、光沢層が遮光層よりも上層に形成されてなることを特徴とする。
【0015】
【作用】
本発明の調理器用トッププレートは、透明低膨張ガラス板の表面に光沢層及び遮光層を含む装飾層が形成されてなる調理器用トッププレートであって、装飾層が実質的に貴金属元素を含まず、光沢層が遮光層よりも上層に形成されてなるため、金属光沢を有し、リサイクル性に優れ、一種類のガラス生地で多色化を達成することができる。すなわち、光沢層により金属光沢を付与することができ、光沢層が可視光を透過することが出来るため、光沢層の下層にある遮光層の色調を変えるだけで、トッププレートの色調を変えることができるとともに、遮光層による色調と光沢層による金属光沢とが相まって、独特の色を創造できるようになる。特に、光沢層が、化学蒸着法(CVD)、物理蒸着法、イオンプレーティング法、スパッタ法等の蒸着法によって形成されてなると、金属光沢が得やすいため好ましい。また、光沢層を構成する膜の数、膜材質又は膜厚を調整し、波長による反射率のプロファイルを変えることによって、金属光沢の程度や色調が調整可能となる。また、調理器用トッププレートをガラス原料としてリサイクルした際に、ガラスが着色したり、ブツ等のガラス欠陥が発生したりすることがなく、不均質な結晶化が起こることもない。
【0016】
尚、光沢層が遮光層よりも上層に形成されてなるとは、調理器用トッププレートを調理器にセットした状態で、光沢層が遮光層より使用者側に形成されていることを意味する。
【0017】
また、本発明の調理器用トッププレートは、電磁加熱調理器用トッププレートとして使用した場合に、印加される電力量を表示するインジケータをトッププレートの非使用側に設けても、インジケータを表面から明瞭に視認することができ、トッププレートに穴をあける必要がなく、トッププレートが欠けたりあるいは割れたりすることがない。また、遮光層の可視光透過率が低い場合であっても、インジケータと対向する部分に遮光層を形成しないようにすれば、インジケータを表面から明瞭に視認することができる。
【0018】
また、本発明の調理器用トッププレートは、装飾層が、実質的にPb元素を含有していないと、有害なPb元素が含まれないため、環境上好ましい。特に、光沢層と遮光層の少なくとも一方、好ましくは装飾層が、透明低膨張ガラス板に含まれる元素と同じ元素のうち少なくとも1種類の元素を合量で50質量%以上、好ましくは70質量%以上含有すると、調理器用トッププレートをガラス原料として再溶融しても、透明低膨張ガラス板の着色や特性を変化させにくいため、リサイクル性に優れる。尚、装飾層に含まれる元素のうち、窒素、硫黄及びハロゲンは、リサイクル時にそれらの大部分がガスとなって放出され、ガラス中に残存せず、ガラスの着色や特性変化に影響がないため、これらの元素は、低膨張ガラス板に含まれる元素と同じ元素として取り扱う。
【0019】
光沢層は、透明低膨張ガラス板の裏面に形成してなると、膜剥がれがなく好ましいが、特に、スパッタ法により形成した光沢層は、平滑で、より緻密な構造を有し、ガラス表面に強固に形成されるため、透明低膨張ガラス板の表面(使用面)に形成しても、使用面に付着した食品、調味料等の汚れを、簡単に除去することができ、あるいは、汚れを落とすために、クレンザーやブラシを使っても、耐摩耗性に優れるため、膜が剥がれにくい。
【0020】
光沢層は、一層以上の蒸着膜から構成され、少なくとも一層の蒸着膜が、Ti、Si、Zr、Nb、W及びTaの群から選択された一種の酸化物もしくは窒化物を含むと、光沢層と低膨張ガラス板もしくは遮光層との屈折率差によって、光の干渉作用が大きくなり、金属光沢を得やすく、耐熱性に優れる。特に、光沢層が、Ti又はZrの酸化物膜とSiの酸化物膜が交互に2〜8層積層されてなると、金属光沢を得やすくなると共に、それらの膜厚の調整によって、トッププレートの光沢や色調の調整がしやすく、リサイクル性に優れる。また、耐熱性にもさらに優れるため、電磁調理器だけでなく、ラジアントヒーターやハロゲンヒーター等の赤外線調理器のトッププレートとして好適である。
【0021】
光沢層は、具体的には、低膨張ガラス側から、20〜100nmのSiO2膜、100〜200nmのTiO2又はZrO2膜、20〜100nmのSiO2膜及び100〜200nmのTiO2又はZrO2膜からなる4層の蒸着膜、あるいは、20〜100nmのSiO2膜、100〜200nmのTiO2又はZrO2膜、20〜100nmのSiO2膜、100〜200nmのTiO2又はZrO2膜、20〜100nmのSiO2膜及び100〜200nmのTiO2又はZrO2膜からなる6層の蒸着膜からなると、可視光の透過率が高く、遮光層の色調が光沢層を通して視認しやすいため好ましい。
【0022】
遮光膜は、透明低膨張ガラス板の裏面(非使用面)に形成されてなると、膜かがれがなく好ましい。
【0023】
また、遮光層としては、無機顔料膜、ラスター膜もしくは耐熱塗料膜が使用可能であるが、特に無機顔料膜であると、遮光性や耐熱性に優れるため好ましい。
【0024】
また、遮光層が、無機顔料成分とガラス成分を含有する無機顔料膜からなると、無機顔料の種類や含有量を変化させることによって、濃色だけでなく薄色も出すことができ、自由に色調を調整できるため好ましい。
【0025】
また、無機顔料膜が低膨張ガラス板の非使用面に形成されてなる場合には、無機顔料膜が、質量%で、ガラス成分を10〜70%、好ましくは20〜50%含むと、多孔質の膜を得やすく、熱膨張差による遮光膜のクラック発生を防止しやすいため、使用面からの荷重によって調理器用トッププレートが破損しにくい。ガラス成分が10%よりも少ないと、無機顔料成分を低膨張ガラス板に強固に固定することが出来ずに剥がれやすく、70%よりも多いと、膜が緻密になりすぎて、熱膨張差によって遮光膜にクラックが発生しやすくなるため好ましくない。
【0026】
また、無機顔料膜は、実質的にPb元素を含有していないと、環境上好ましく、無機顔料膜の熱膨張係数が大きくなりにくくなるため好ましい。具体的に、無機顔料膜が、ガラス成分として、B23−SiO2系、Na2O−CaO−SiO2系、Li2O−Al23−SiO2系、ZnO−Al23−P25系等のガラスを使用できるが、特に、ガラス成分が、質量%で、SiO2 55〜72%、Al23 4〜8%、B23 14〜22%、BaO 2〜4%、Na2O 5.1〜15%、Li2O 0〜2%、K2O 0〜2.8%、F2 0〜2%の組成を有すると、熱膨張係数が小さく、化学的耐久性に優れると共に、遮光層として充分な機械的強度が得やすいため好ましい。
【0027】
無機顔料としては、TiO2、ZrO2、ZrSiO4の他、Co−Al−Zn系、Co−Al−Si系、Co−Al−Ti系、Co−Al−Cr系、Co−Ni−Ti−Zn系、Ti−Sb−Cr系、Ti−Ni系、Co−Si系、Ti−Fe−Zn系、Fe−Zn系、Fe−Ni−Cr系、Zn−Fe−Cr−Al系、Co−Cr−Fe系、Cu−Cr系、Cu−Cr−Fe系、Cu−Cr−Mn系の酸化物顔料等を単独又は混合して用いることができる。また、無機顔料として、マイカ(雲母)を含む顔料を用いると、さらに光沢が増すため好ましい。
【0028】
無機顔料膜は、無機顔料成分やガラス成分以外にも、必要に応じてフィラーを添加できる。
【0029】
遮光層は、膜厚が0.1〜50μm、特に0.2〜40μmであることが好ましい。膜厚が0.1μmよりも薄いと、可視光の遮蔽が困難であり、内部構造が使用者から見えてしまう。また、50μmよりも厚くしても、可視光の遮蔽の効果が変らず、不経済であり、また、トッププレートのリサイクル性が悪くなるため好ましくない。
【0030】
また、遮光層が、スクリーン印刷法によって低膨張ガラス板に印刷・焼付されてなると、簡便で安価となるため好ましい。
【0031】
また、遮光層が、ラジエントヒーターもしくはハロゲンヒーターと対向するトッププレート基板表面部分の全部又は一部の領域に形成されていないと、ラジエントヒーターもしくはハロゲンヒーターの赤外線が透過しやすく、熱が調理器内部に篭りにくいため好ましい。また、光沢層は、ラジエントヒーターもしくはハロゲンヒーターと対向するトッププレート基板表面部分の全部又は一部の領域に形成されていなくてもよい。
【0032】
また、本発明の調理器用トッププレートは、透明低膨張ガラス板が、波長0.4〜0.8μmの可視光領域における平均透過率が3mm厚で50%以上、好ましくは70%以上である低膨張ガラスからなると、遮光層を透明低膨張ガラスの裏面に形成した場合、遮光層の色調が透明低膨張ガラス板を透過して見えるため好ましい。
【0033】
また、透明低膨張ガラス板が、600℃からの急冷に耐える、いわゆる耐熱衝撃性が高い低膨張ガラスであれば使用することができ、具体的には、30〜500℃における平均熱膨張係数が50×10-7/℃以下のガラスが好適であり、例えば、ホウケイ酸塩ガラス、石英ガラス、β−石英固溶体を主結晶とする透明低膨張結晶化ガラスが使用可能である。特に、透明低膨張ガラス板が、30〜500℃における平均熱膨張係数が−10〜+30×10-7/℃、さらに好ましくは−10〜+20×10-7/℃の透明低膨張結晶化ガラスからなると、トッププレートの耐熱衝撃性がさらに高くなり、加熱時にトッププレートの温度分布が大きくなっても、ストレスが発生しにくく割れ難いため好ましい。
【0034】
透明低膨張結晶化ガラスは、Si、Al、Li及び酸素を必須元素として含有し、且つ、Ti、Zr、Sn、B、Zn、P、As、Sb、アルカリ金属元素、アルカリ土類金属元素、硫黄、窒素及びハロゲンからなる群から選ばれた1種類以上の元素を含有し、具体的には、質量%で、SiO2 50〜80%、Al23 12〜30%、Li2O 1〜6%、MgO 0〜5%、ZnO 0〜5%、BaO 0〜8%、Na2O 0〜5%、K2O 0〜5%、TiO2 0〜8%、ZrO2 0〜7%、P25 0〜7%、Sb23 0〜4%、As23 0〜2%であると、透明で、30〜500℃における平均熱膨張係数が−10〜+30×10-7/℃となりやすいため好ましい。
【0035】
【実施例】
本発明の調理器用トッププレートを、実施例に基づいて詳細に説明する。
【0036】
表1〜3は、本発明の実施例1〜10を、表4は、比較例1〜3を示す。また、図1は、実施例1〜4の調理器用トッププレートの説明図、図2は、実施例5〜10の調理器用トッププレートの説明図である。
【0037】
【表1】

Figure 2004193050
【0038】
【表2】
Figure 2004193050
【0039】
【表3】
Figure 2004193050
【0040】
【表4】
Figure 2004193050
【0041】
図1、2に示すように、30〜500℃における平均線熱膨張係数が−5×10-7/℃である透明結晶化ガラスからなる基板11上に、表1〜3に示す膜材質と膜厚になるようにスパッタ法による光沢層12と、スクリーン印刷法による遮光層13とからなる装飾層14を形成し、実施例1〜10の調理器用トッププレート10を作製した。尚、上記結晶化ガラスは、質量%で、SiO2 66%、Al23 22%、Li2O 4%、TiO2 2%、ZrO2 2%、BaO 1.5%、Na2O 0.5%、K2O 0.5 %、P25 1%、As23 0.4%、Sb23 0.1%の組成を有し、厚さ3mmで、波長0.4〜0.8μmにおいて、85%の透過率を有するものである。また、実施例1〜4の遮光層13は、ガラスフリット80質量%と無機顔料20質量%からなる混合物100質量部に対して、また、実施例5〜10の遮光層13は、ガラスフリット20質量%と無機顔料80質量%からなる混合物100質量部に対して、アクリル系の有機バインダー60質量部を加え、印刷しやすい粘度となるように、ブチルカルビトールアセテートをさらに添加して作製したペーストをスクリーン印刷で透明結晶化ガラスからなる基板11上に印刷し、800℃で20分間焼成して形成した。尚、ガラスフリットは、質量%で、SiO2 63%、B23 19%、Al23 6%、Na2O 6%、K2O 2%、Li2O 2%、BaO 2%の組成を有するものを使用した。また、無機顔料として、橙色顔料は、質量%で、TiO2 70%、Sb23 15%、NiO 15%の組成を有し、グレー色顔料は、質量%で、TiO2 80%、Co34 7%、Cr23 7%、Fe23 6%の組成を有するものを使用した。
【0042】
比較例1は、実施例と同じ透明結晶化ガラスからなる基板上に、金色となるAuを含有するラスターペースト(GG−5566)を250メッシュのスクリーンを用いて塗布し、乾燥後、830℃にて焼き付け、調理器用トッププレートを作製した。
【0043】
比較例2は、シルバー色となるPdを含有するラスターペースト(GP−5566)を用いた以外は、比較例1と同様にして調理器用トッププレートを作製した。
【0044】
比較例3は、Co34 40%、Cr23 30%、Fe23 30%の組成を有する黒色顔料を用いた以外は、実施例の遮光層と同様にして遮光膜を形成し、調理器用トッププレートを作製した。
【0045】
表中の光沢層リサイクル%、遮光層リサイクル%又は装飾層リサイクル%とは、光沢層、遮光層又は装飾層を構成する元素が、結晶化ガラス中に含まれる元素と同じ元素の合量を質量%で表したものであり、光沢層リサイクル%、遮光層リサイクル%又は装飾層リサイクル%が高いほどリサイクル性に優れることを示す。
【0046】
また、リサイクル時のガラスの変色の有無は、膜付けされた調理器用トッププレート500gを入れた300mlの石英ビーカーを電気炉中で1600℃、10時間溶融し、カーボン台に流し出し、成形ローラーを用いて、厚さ5mmのガラス板を作製した。尚、溶融中には、数回攪拌を行った。このガラス板を比較用ガラス板(未結晶化の再溶融する前の板)とともに、3mm厚に光学研磨し、両者を並べて肉眼で目視により評価し、色差がない場合を「なし」、ある場合を「あり」とした。
【0047】
また、リサイクル時の異物の有無は、変色の有無の評価と同じサンプルを用い、50g中に5μm以上の大きさの異物の有無を、光学顕微鏡で観察して評価した。また、リサイクル時の不均質結晶化の有無は、上記のように再溶融して成形したガラス板を、750℃で3時間し、その後900℃で1時間熱処理して結晶化させ、再溶融前の基板とともに、3mm厚に光学研磨し、両者を並べて肉眼で目視により評価し、両者に色差がなく、白濁などの結晶化の異常が見られない場合を「なし」とし、色差や結晶化の異常が見られる場合を「あり」とした。
【0048】
表1〜3からわかるように、実施例1〜10は、光沢を有し、リサイクル時においても、ガラスの着色、異物、不均質結晶化のいずれも発生しなかった。
一方、表4からわかるように、比較例1は、光沢を有しているものの、リサイクル時に、ガラスの着色、異物、不均質結晶化が見られた。また、比較例2は、光沢を有しているもの、異物、不均質結晶化が見られた。また、比較例3は、光沢が無く、さらに、リサイクル時にガラスの着色が見られた。
【0049】
【効果】
以上説明したように、本発明の調理器用トッププレートは、金属光沢を有し、リサイクル性に優れ、一種類のガラス生地で多色化を達成することができるため、ラジエントヒーターやハロゲンヒーターを用いた赤外線加熱調理器、電磁加熱(IH)調理器、ガス調理器のトッププレートとして好適である。
【図面の簡単な説明】
【図1】本発明における実施例1〜4の調理器用トッププレートの説明図である。
【図2】本発明における実施例5〜10の調理器用トッププレートの説明図である。
【符号の説明】
10 調理器用トッププレート
11 基板
12 光沢層
13 遮光層
14 装飾層[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a cooker top plate.
[0002]
[Prior art]
As cooking appliances for home and business use, not only conventional gas stoves, but also infrared heating appliances and electromagnetic heating (IH) appliances using a radiant heater or a halogen heater have come to be used.
[0003]
For the top plate used in the electromagnetic heating cooker, materials such as glass, ceramics, crystallized glass, which have a small amount of electromagnetic induction heating and low thermal expansion, are used in terms of thermal efficiency, safety, and thermal shock resistance. .
[0004]
Conventionally, even in gas cookers that used enamel or stainless steel as the top plate, these materials are excellent in aesthetics and cleanability, so non-metallic materials such as low thermal expansion glass, ceramics, and crystallized glass Materials have come to be used.
[0005]
The cooker top plate not only prevents splashing of water, seasonings, food, etc. into the heating device, but also conceals the internal structure of the cooking device, such as the heating device and wiring, and improves the appearance. It has also been required to do so.
[0006]
The first method for concealing the internal structure of a cooking device using a nonmetallic material for the top plate is a low expansion crystallized glass that is colored deeply with a metal transition element as a cooking device top plate, for example, And GC-190 made by Nippon Electric Glass Co., Ltd. or serane made by Shot.
[0007]
The second method is a method of forming a light shielding film on the surface of transparent low expansion glass by using a printing method. Specifically, a top plate in which a film made of glass and an inorganic pigment is provided as a light-shielding film on a transparent low-expansion crystallized glass surface (for example, see Patent Document 1). Since the light-shielding film has a higher thermal expansion coefficient than a substrate made of low-expansion crystallized glass, by making the film porous, generation of cracks in the film is suppressed. There is also known a top plate in which a raster-colored film made of a noble metal and a base metal is provided as a light-shielding film on the surface of a transparent low expansion crystallized glass (for example, see Patent Document 2).
[0008]
In recent years, with the spread of stainless steel worktops and kitchens, those with a metallic luster are required so that the cooker top plate is in harmony with the surrounding worktops and kitchens. Since the top plate has a metallic luster, it can also satisfy this requirement.
[0009]
[Patent Document 1]
JP-A-10-273342 [Patent Document 2]
Japanese Patent Publication No. Hei 7-17409
[Problems to be solved by the invention]
However, in order to achieve top plate multi-coloring by the first method, it is necessary to prepare various types of glass fabrics according to the number of colors and color densities, which not only increases the cost but also is suitable for glass Since transition metal elements are also limited, there is a limit in producing various colors. In addition, in the case of a top plate of an electromagnetic heating cooker, if it is desired to provide an indicator for displaying an applied electric energy, it is necessary to make a hole in the top plate, and the top plate is easily chipped or broken. Therefore, it is not preferable.
[0011]
Further, in the second method, the cooker top plate described in Patent Document 1 does not have a metallic luster and cannot be harmonized with a stainless steel worktop or a cooking room, and the light-shielding layer has a crystal structure. Since the glass plate contains a large amount of components different from those of the glass substrate, there is a possibility that the color tone and characteristics of the crystallized glass substrate may be changed when the top plate on which the light shielding layer is formed is recycled as a glass material.
[0012]
Further, the cooker top plate described in Patent Literature 2 can produce dark colors such as black, dark blue, and copper, depending on the raster color, but the number of colors is small. In addition, when the top plate for a cooker is recycled as a glass material, not only does the glass become colored or glass defects such as lumps occur, but crystallization near the lumps is promoted, resulting in uneven crystallization. Occurs, causing partial discoloration or cloudiness, resulting in aesthetic and strength problems. That is, when the top plate for a cooker is recycled as a glass raw material, when the noble metal constituting the light-shielding film formed on the top plate for the cooker is mixed with the glass, the noble metal is present in the glass as ions, colloids, and the like. This causes a color change of the glass, and in some cases, exists as a foreign matter in the glass, and further, the foreign matter may be used as a crystal nucleus, and crystallization may abnormally proceed around the foreign matter. . Further, if the light-shielding film is removed by polishing or the like and the glass material alone is melted again as a glass raw material, not only costs are increased, but also polishing powder containing a noble metal is generated. Even if the noble metal is removed, this abrasive powder contains a large amount of an abrasive, so that it is difficult to recycle the raw material as a glass material, and it is likely to be discarded and become an environmental burden.
[0013]
An object of the present invention has been made in view of the above problems, and provides a top plate for a cooker that has a metallic luster, is excellent in recyclability, and can achieve multicoloring with one type of glass cloth. It is.
[0014]
[Means for Solving the Problems]
The cooker top plate of the present invention is a cooker top plate in which a decorative layer including a gloss layer and a light-shielding layer is formed on the surface of a transparent low-expansion glass plate, and the decorative layer does not substantially include a noble metal element. The glossy layer is formed above the light-shielding layer.
[0015]
[Action]
The cooker top plate of the present invention is a cooker top plate in which a decorative layer including a gloss layer and a light-shielding layer is formed on the surface of a transparent low-expansion glass plate, and the decorative layer does not substantially include a noble metal element. Since the glossy layer is formed above the light-shielding layer, it has metallic luster, is excellent in recyclability, and can achieve multicoloring with one kind of glass fabric. That is, since the glossy layer can impart metallic luster and the glossy layer can transmit visible light, the color tone of the top plate can be changed only by changing the color tone of the light shielding layer below the glossy layer. In addition, the color tone of the light-shielding layer and the metallic luster of the glossy layer combine to create a unique color. In particular, it is preferable that the gloss layer be formed by a vapor deposition method such as a chemical vapor deposition method (CVD), a physical vapor deposition method, an ion plating method, or a sputtering method, because it is easy to obtain a metallic luster. Further, by adjusting the number, film material or film thickness of the films constituting the gloss layer and changing the reflectance profile depending on the wavelength, the degree and color tone of the metallic gloss can be adjusted. Further, when the cooker top plate is recycled as a glass raw material, the glass is not colored, glass defects such as bumps are not generated, and non-uniform crystallization does not occur.
[0016]
Here, that the gloss layer is formed above the light-shielding layer means that the gloss layer is formed on the user side of the light-shielding layer with the cooker top plate set in the cooker.
[0017]
Further, when the cooker top plate of the present invention is used as a top plate for an electromagnetic heating cooker, even if an indicator for displaying the applied electric energy is provided on the non-use side of the top plate, the indicator is clearly seen from the surface. It is visible, there is no need to drill holes in the top plate, and the top plate is not chipped or cracked. In addition, even when the visible light transmittance of the light-shielding layer is low, if the light-shielding layer is not formed in a portion facing the indicator, the indicator can be clearly seen from the surface.
[0018]
Moreover, the top plate for a cooker of the present invention is environmentally preferable because the harmful Pb element is not contained when the decorative layer does not substantially contain the Pb element. In particular, at least one of the gloss layer and the light-shielding layer, preferably the decoration layer, comprises at least one of the same elements as the elements contained in the transparent low expansion glass plate in a total amount of 50% by mass or more, preferably 70% by mass. When it is contained as described above, even if the top plate for a cooker is re-melted as a glass raw material, the coloring and the properties of the transparent low expansion glass plate are not easily changed, so that the recyclability is excellent. Of the elements contained in the decorative layer, most of nitrogen, sulfur, and halogen are released as gas during recycling, do not remain in the glass, and do not affect the coloring or change in properties of the glass. These elements are treated as the same elements as those contained in the low expansion glass plate.
[0019]
The gloss layer is preferably formed on the back surface of the transparent low-expansion glass plate without peeling off the film. In particular, the gloss layer formed by the sputtering method has a smooth, more dense structure, and is firmly attached to the glass surface. Therefore, even if it is formed on the surface (use surface) of the transparent low-expansion glass plate, it is possible to easily remove dirt such as foods and seasonings adhered to the use surface, or to remove dirt. Therefore, even if a cleanser or a brush is used, the film is hardly peeled off because of its excellent wear resistance.
[0020]
The glossy layer is composed of one or more vapor-deposited films, and when at least one vapor-deposited film contains a kind of oxide or nitride selected from the group consisting of Ti, Si, Zr, Nb, W and Ta, the glossy layer is formed. Due to the difference in refractive index between the glass substrate and the low-expansion glass plate or the light-shielding layer, the interference effect of light increases, so that a metallic luster is easily obtained and the heat resistance is excellent. In particular, when the gloss layer is formed by alternately laminating 2 to 8 oxide films of Ti or Zr and an oxide film of Si, it becomes easy to obtain a metallic luster and the thickness of the top plate can be adjusted by adjusting their film thickness. It is easy to adjust gloss and color tone and has excellent recyclability. Further, since it is further excellent in heat resistance, it is suitable as a top plate not only for an electromagnetic cooker but also for an infrared cooker such as a radiant heater or a halogen heater.
[0021]
Gloss layer, specifically, the low expansion glass side, the SiO 2 film of 20 to 100 nm, TiO 2 or ZrO 2 film 100 to 200 nm, TiO 2 or ZrO of SiO 2 film and 100 to 200 nm of 20 to 100 nm 4-layer deposited film composed of 2 film, or, SiO 2 film of 20 to 100 nm, TiO 2 or ZrO 2 film 100 to 200 nm, SiO 2 film of 20 to 100 nm, TiO 2 or ZrO 2 film 100 to 200 nm, When made of a SiO 2 film and a 100~200nm of TiO 2 or ZrO 2 film 6-layered deposited film consisting of 20 to 100 nm, high visible light transmittance is preferable because the color tone of the light-shielding layer is easily visible through the glossy layer.
[0022]
The light-shielding film is preferably formed on the back surface (non-use surface) of the transparent low-expansion glass plate because the film does not peel off.
[0023]
As the light-shielding layer, an inorganic pigment film, a raster film, or a heat-resistant paint film can be used. In particular, an inorganic pigment film is preferable because of excellent light-shielding properties and heat resistance.
[0024]
In addition, when the light-shielding layer is made of an inorganic pigment film containing an inorganic pigment component and a glass component, not only a dark color but also a light color can be obtained by changing the type and content of the inorganic pigment, and the color tone can be freely adjusted. It is preferable because it can be adjusted.
[0025]
When the inorganic pigment film is formed on the non-use surface of the low expansion glass plate, if the inorganic pigment film contains 10 to 70%, preferably 20 to 50% of a glass component by mass%, the porous film becomes porous. It is easy to obtain a high quality film, and it is easy to prevent cracks in the light shielding film due to a difference in thermal expansion. Therefore, the top plate for a cooker is hardly damaged by a load from the use surface. If the glass component is less than 10%, the inorganic pigment component cannot be firmly fixed to the low-expansion glass plate and tends to peel off. If the glass component is more than 70%, the film becomes too dense, resulting in a difference in thermal expansion. It is not preferable because cracks easily occur in the light shielding film.
[0026]
Further, it is preferable that the inorganic pigment film does not substantially contain the Pb element because it is environmentally preferable and the coefficient of thermal expansion of the inorganic pigment film is hardly increased. Specifically, the inorganic pigment film is composed of B 2 O 3 —SiO 2 , Na 2 O—CaO—SiO 2 , Li 2 O—Al 2 O 3 —SiO 2 , and ZnO—Al 2 O as glass components. 3 is a glass -P 2 O 5 system and the like can be used, in particular, glass component, in terms of mass%, SiO 2 55~72%, Al 2 O 3 4~8%, B 2 O 3 14~22%, When having a composition of BaO 2-4%, Na 2 O 5.1-15%, Li 2 O 0-2%, K 2 O 0-2.8%, and F 2 0-2%, the thermal expansion coefficient becomes It is preferable because it is small, has excellent chemical durability, and easily obtains sufficient mechanical strength as a light shielding layer.
[0027]
Examples of the inorganic pigment include TiO 2 , ZrO 2 , ZrSiO 4 , Co-Al-Zn, Co-Al-Si, Co-Al-Ti, Co-Al-Cr, and Co-Ni-Ti-. Zn-based, Ti-Sb-Cr-based, Ti-Ni-based, Co-Si-based, Ti-Fe-Zn-based, Fe-Zn-based, Fe-Ni-Cr-based, Zn-Fe-Cr-Al-based, Co- Cr-Fe-based, Cu-Cr-based, Cu-Cr-Fe-based, Cu-Cr-Mn-based oxide pigments and the like can be used alone or in combination. Further, it is preferable to use a pigment containing mica (mica) as the inorganic pigment because the gloss is further increased.
[0028]
A filler can be added to the inorganic pigment film as needed in addition to the inorganic pigment component and the glass component.
[0029]
The light-shielding layer preferably has a thickness of 0.1 to 50 μm, particularly 0.2 to 40 μm. If the thickness is less than 0.1 μm, it is difficult to shield visible light, and the internal structure is visible to the user. Further, if the thickness is more than 50 μm, the effect of shielding visible light does not change, which is uneconomical, and the recyclability of the top plate deteriorates, which is not preferable.
[0030]
Further, it is preferable that the light-shielding layer is printed and baked on a low expansion glass plate by a screen printing method, because it is simple and inexpensive.
[0031]
In addition, if the light-shielding layer is not formed on all or a part of the surface of the top plate substrate facing the radiant heater or the halogen heater, infrared rays of the radiant heater or the halogen heater are easily transmitted, and heat is generated inside the cooking device. It is preferable because it is difficult to stay inside. Further, the gloss layer may not be formed on all or a part of the surface of the top plate substrate facing the radiant heater or the halogen heater.
[0032]
Further, in the cooker top plate of the present invention, the transparent low-expansion glass plate has an average transmittance in a visible light region of a wavelength of 0.4 to 0.8 μm of 3 mm in thickness of 50% or more, preferably 70% or more. It is preferable that the light-shielding layer is formed of an expanding glass, since the color tone of the light-shielding layer is visible through the transparent low-expansion glass plate when the light-shielding layer is formed on the back surface of the transparent low-expansion glass.
[0033]
Further, a transparent low-expansion glass plate can be used as long as it is a low-expansion glass having high so-called thermal shock resistance that withstands rapid cooling from 600 ° C. Specifically, the average thermal expansion coefficient at 30 to 500 ° C. Glass having a density of 50 × 10 −7 / ° C. or less is suitable. For example, a transparent low-expansion crystallized glass having a main crystal of borosilicate glass, quartz glass, and β-quartz solid solution can be used. In particular, the transparent low-expansion glass plate has an average thermal expansion coefficient at −30 to 500 ° C. of −10 to + 30 × 10 −7 / ° C., and more preferably −10 to + 20 × 10 −7 / ° C. Is preferable because the thermal shock resistance of the top plate is further increased, and even if the temperature distribution of the top plate becomes large during heating, stress is hardly generated and the top plate is hardly broken.
[0034]
The transparent low-expansion crystallized glass contains Si, Al, Li and oxygen as essential elements, and has Ti, Zr, Sn, B, Zn, P, As, Sb, an alkali metal element, an alkaline earth metal element, sulfur, one or more elements selected from the group consisting of nitrogen and halogen containing, specifically, in mass%, SiO 2 50~80%, Al 2 O 3 12~30%, Li 2 O 1 ~6%, 0~5% MgO, 0~5 % ZnO, BaO 0~8%, Na 2 O 0~5%, K 2 O 0~5%, TiO 2 0~8%, ZrO 2 0~7 %, P 2 O 5 0~7% , Sb 2 O 3 0~4%, When it is As 2 O 3 0~2%, clear, average thermal expansion coefficient of -10 to + 30 × at 30 to 500 ° C. This is preferable because it is likely to be 10 -7 / ° C.
[0035]
【Example】
The cooker top plate of the present invention will be described in detail based on examples.
[0036]
Tables 1 to 3 show Examples 1 to 10 of the present invention, and Table 4 shows Comparative Examples 1 to 3. FIG. 1 is an explanatory view of a cooker top plate of Examples 1 to 4, and FIG. 2 is an explanatory view of cooker top plates of Examples 5 to 10.
[0037]
[Table 1]
Figure 2004193050
[0038]
[Table 2]
Figure 2004193050
[0039]
[Table 3]
Figure 2004193050
[0040]
[Table 4]
Figure 2004193050
[0041]
As shown in FIGS. 1 and 2, on a substrate 11 made of transparent crystallized glass having an average linear thermal expansion coefficient at −30 to 500 ° C. of −5 × 10 −7 / ° C., The decorative layer 14 composed of the gloss layer 12 by the sputtering method and the light shielding layer 13 by the screen printing method was formed so as to have a film thickness, and the cooker top plates 10 of Examples 1 to 10 were produced. The crystallized glass is, by mass%, SiO 2 66%, Al 2 O 3 22%, Li 2 O 4%, TiO 2 2%, ZrO 2 2%, BaO 1.5%, Na 2 O 0 It has a composition of 0.5%, K 2 O 0.5%, P 2 O 5 1%, As 2 O 3 0.4% and Sb 2 O 3 0.1%. It has a transmittance of 85% at 4 to 0.8 μm. The light-shielding layer 13 of each of Examples 1 to 4 is based on 100 parts by mass of a mixture composed of 80% by mass of glass frit and 20% by mass of an inorganic pigment. A paste prepared by adding 60 parts by mass of an acrylic organic binder to 100 parts by mass of a mixture consisting of 80% by mass of an inorganic pigment and 80% by mass of an inorganic pigment, and further adding butyl carbitol acetate so as to have a printable viscosity. Was printed on the substrate 11 made of transparent crystallized glass by screen printing and baked at 800 ° C. for 20 minutes. The glass frit is a mass%, SiO 2 63%, B 2 O 3 19%, Al 2 O 3 6%, Na 2 O 6%, K 2 O 2%, Li 2 O 2%, BaO 2% The one having the following composition was used. Further, as the inorganic pigment, an orange pigment, mass%, TiO 2 70%, Sb 2 O 3 15%, has a composition of NiO 15%, gray pigments, in mass%, TiO 2 80%, Co 3 O 4 7%, Cr 2 O 3 7%, was used having a Fe 2 O 3 of 6% composition.
[0042]
In Comparative Example 1, a raster paste (GG-5566) containing Au which becomes gold was applied using a 250-mesh screen on a substrate made of the same transparent crystallized glass as in the example, dried, and then heated to 830 ° C. To make a cooker top plate.
[0043]
In Comparative Example 2, a cooker top plate was produced in the same manner as in Comparative Example 1, except that a raster paste (GP-5566) containing Pd, which became silver, was used.
[0044]
In Comparative Example 3, a light-shielding film was formed in the same manner as the light-shielding layer of the example except that a black pigment having a composition of 40% Co 3 O 4 , 30% Cr 2 O 3, and 30% Fe 2 O 3 was used. Then, a cooker top plate was prepared.
[0045]
The gloss layer recycling%, shading layer recycling% or decoration layer recycling% in the table means the total amount of the elements constituting the gloss layer, the shading layer or the decoration layer and the same elements as those contained in the crystallized glass. %, And the higher the gloss layer recycling%, light-shielding layer recycling% or decoration layer recycling%, the higher the recyclability.
[0046]
In addition, the presence or absence of discoloration of the glass at the time of recycling is determined by melting a 300 ml quartz beaker containing 500 g of a cooked top plate with a film in an electric furnace at 1600 ° C. for 10 hours, pouring the mixture onto a carbon table, and setting a forming roller. A glass plate having a thickness of 5 mm was manufactured using the glass plate. In addition, stirring was performed several times during melting. This glass plate was optically polished to a thickness of 3 mm together with a comparative glass plate (an uncrystallized plate before re-melting), and both were side-by-side and visually evaluated with naked eyes. Is "Yes".
[0047]
The presence or absence of foreign matter at the time of recycling was evaluated by observing the presence or absence of foreign matter having a size of 5 μm or more in 50 g with an optical microscope, using the same sample as that for evaluating the presence or absence of discoloration. The presence or absence of heterogeneous crystallization at the time of recycling can be determined by re-melting and shaping the glass plate as described above at 750 ° C. for 3 hours, and then heat-treating it at 900 ° C. for 1 hour to crystallize it. Optically polished to a thickness of 3 mm together with the substrate, and the two were lined up and evaluated visually with the naked eye. If there was no color difference between the two and no abnormal crystallization such as cloudiness was observed, it was regarded as “none”, and the color difference and crystallization The case where an abnormality was observed was defined as “Yes”.
[0048]
As can be seen from Tables 1 to 3, Examples 1 to 10 were glossy and did not cause any of glass coloring, foreign matter, or heterogeneous crystallization even during recycling.
On the other hand, as can be seen from Table 4, Comparative Example 1 had gloss, but at the time of recycling, glass coloring, foreign matter, and heterogeneous crystallization were observed. In Comparative Example 2, glossiness, foreign matter, and heterogeneous crystallization were observed. In Comparative Example 3, there was no gloss, and further, coloring of the glass was observed at the time of recycling.
[0049]
【effect】
As described above, the cooker top plate of the present invention has a metallic luster, is excellent in recyclability, and can achieve multicoloring with one type of glass cloth. It is suitable as a top plate for an infrared heating cooker, an electromagnetic heating (IH) cooker, and a gas cooker.
[Brief description of the drawings]
FIG. 1 is an explanatory view of a cooker top plate according to Examples 1 to 4 of the present invention.
FIG. 2 is an explanatory view of cooker top plates of Examples 5 to 10 according to the present invention.
[Explanation of symbols]
DESCRIPTION OF SYMBOLS 10 Top plate for cookers 11 Substrate 12 Gloss layer 13 Light shielding layer 14 Decorative layer

Claims (14)

透明低膨張ガラス板の表面に光沢層及び遮光層を含む装飾層が形成されてなる調理器用トッププレートであって、装飾層が実質的に貴金属元素を含まず、光沢層が遮光層よりも上層に形成されてなる調理器用トッププレート。A top plate for a cooker in which a decoration layer including a gloss layer and a light-shielding layer is formed on a surface of a transparent low-expansion glass plate, wherein the decoration layer contains substantially no noble metal element, and the gloss layer is an upper layer than the light-shielding layer. Top plate for cooker formed on. 光沢層が、蒸着法によって形成されてなる請求項1に記載の調理器用トッププレート。The cooker top plate according to claim 1, wherein the glossy layer is formed by a vapor deposition method. 蒸着法がスパッタ法である請求項2に記載の調理器用トッププレート。The top plate for a cooker according to claim 2, wherein the vapor deposition method is a sputtering method. 装飾層が、実質的にPb元素を含まない請求項1に記載の調理器用トッププレート。The cooker top plate according to claim 1, wherein the decorative layer does not substantially contain a Pb element. 光沢層と遮光層の少なくとも一方が、透明低膨張ガラス板に含まれる元素と同じ元素のうち少なくとも1種類の元素を合量で50質量%以上含有する請求項1又は2に記載の調理器用トッププレート。3. The cooker top according to claim 1, wherein at least one of the glossy layer and the light-shielding layer contains at least one element of the same element as the element contained in the transparent low expansion glass plate in a total amount of 50% by mass or more. plate. 装飾層が、透明低膨張ガラス板に含まれる元素と同じ元素のうち少なくとも1種類の元素を合量で50質量%以上含有する請求項1又は4に記載の調理器用トッププレート。The top plate for a cooker according to claim 1 or 4, wherein the decorative layer contains at least one element of the same element as that contained in the transparent low expansion glass plate in a total amount of 50% by mass or more. 光沢層が、一層以上の蒸着膜から構成され、少なくとも一層の蒸着膜が、Ti、Zr、Si、Ta、W又はNbの酸化物もしくは窒化物を含む請求項1、2及び5のいずれかに記載の調理器用トッププレート。The gloss layer is composed of one or more vapor-deposited films, and at least one of the vapor-deposited films contains an oxide or nitride of Ti, Zr, Si, Ta, W or Nb. A cooker top plate as described. 光沢層が、Ti又はZrの酸化物膜とSiの酸化物膜が交互に2〜8層積層されてなる1、2、5及び7のいずれかに記載の調理器用トッププレート。8. The cooker top plate according to any one of 1, 2, 5, and 7, wherein the glossy layer is formed by alternately stacking two to eight layers of oxide films of Ti or Zr and oxide films of Si. 遮光層が、無機顔料成分及びガラス成分を含有する無機顔料膜からなる請求項1、5及び6のいずれかに記載の調理器用トッププレート。7. The cooker top plate according to claim 1, wherein the light-shielding layer comprises an inorganic pigment film containing an inorganic pigment component and a glass component. 無機顔料膜が透明低膨張ガラス板の非使用面側に形成され、質量%で、ガラス成分を10〜70%含有する請求項9に記載の調理器用トッププレート。The cooker top plate according to claim 9, wherein the inorganic pigment film is formed on the non-use surface side of the transparent low-expansion glass plate, and contains 10 to 70% by mass of a glass component. 無機顔料膜が、ガラス成分が、質量%で、SiO2 55〜72%、Al23 4〜8%、B23 14〜22%、BaO 2〜4%、Na2O 5.1〜15%、Li2O 0〜2%、K2O 0〜2.8%、F2 0〜2%の組成を有する請求項9又は10に記載の調理器用トッププレート。In the inorganic pigment film, 55% to 72% of SiO 2 , 4% to 8% of Al 2 O 3 , 14% to 22% of B 2 O 3 , 2% to 4% of BaO, and 5.1% of Na 2 O by mass% of glass component. ~15%, Li 2 O 0~2% , K 2 O 0~2.8%, top plate for a cooking appliance according to claim 9 or 10 having a composition of F 2 0 to 2%. 透明低膨張ガラス板が、可視光領域における平均透過率が3mm厚で50%以上である低膨張ガラスからなる請求項1、5及び6のいずれかに記載の調理器用トッププレート。7. The top plate for a cooker according to claim 1, wherein the transparent low-expansion glass plate is made of low-expansion glass having an average transmittance in a visible light region of 3 mm and 50% or more. 透明低膨張ガラス板が、30〜70℃における平均熱膨張係数が−10〜+30×10-7/℃である結晶化ガラスからなる請求項1、56及び12のいずれかに記載の調理器用トッププレート。The cooker top according to any one of claims 1, 56 and 12, wherein the transparent low expansion glass plate is made of crystallized glass having an average coefficient of thermal expansion at 30 to 70 ° C of -10 to + 30 × 10 -7 / ° C. plate. 結晶化ガラスが、Si、Al、Li及び酸素を必須元素として含有し、且つ、Ti、Zr、Sn、B、Zn、P、As、Sb、アルカリ金属元素、アルカリ土類金属元素、硫黄、窒素及びハロゲンからなる群から選ばれた1種類以上の元素を含有する請求項13に記載の調理器用トッププレート。The crystallized glass contains Si, Al, Li and oxygen as essential elements, and Ti, Zr, Sn, B, Zn, P, As, Sb, an alkali metal element, an alkaline earth metal element, sulfur, and nitrogen The top plate for a cooker according to claim 13, wherein the top plate contains at least one element selected from the group consisting of: and a halogen.
JP2002362096A 2002-12-13 2002-12-13 Cooker top plate Expired - Fee Related JP4120793B2 (en)

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US7763832B2 (en) 2006-06-16 2010-07-27 Schott Ag Cook top comprising a glass ceramic plate having an opaque coating and an improved window coating on a display window on an underside of the plate
JP2008016318A (en) * 2006-07-06 2008-01-24 Narumi China Corp Glass top plate for electromagnetic cooker, and its manufacturing method
JP2014062733A (en) * 2006-10-16 2014-04-10 Eurokera Snc Glass-ceramic plate and method for manufacturing the same
JP2008192455A (en) * 2007-02-05 2008-08-21 Narumi China Corp Glass top plate for heating cooker
JP2008226608A (en) * 2007-03-12 2008-09-25 Narumi China Corp Glass top plate for cooker
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