JP4188705B2 - Glaze and roof tile - Google Patents

Description

【００４１】
そして、本発明の釉薬としては、Ｒ₂Ｏ（塩基性物質）と燐酸アルミニウムとを多く含有するように構成する。
【００４２】
上記釉薬の製造方法としては、上記基礎釉薬の粉末と、低溶融フリットの粉末と、燐酸アルミニウムの粉末とを混合することにより行う。
【００４３】
本発明の釉薬の使用方法としては、通常の釉薬と同様に、釉薬を水に粉砕分散して液状として素地に施釉した後に焼成する。このようにして窯業製品を製造する。本発明の釉薬は、燐酸アルミニウムを含有しているので、浸透性に優れており、釉薬を素地に施釉すると素地の内部に釉薬が浸透していく。その後焼成を行うと、釉薬と素地が焼き固まる。つまり、素地に浸透した釉薬と素地組成分とが反応して焼き固まる。これにより、本発明の釉薬により形成された釉薬層は、素地の一部にまで浸透した状態となる。
【００４４】
すなわち、図面を利用して説明すると、本発明の釉薬を素地２０に施釉すると素地２０に釉薬層１０が形成される（図１（ａ）参照）。そして、施釉後には、図１（ｂ）に示すように、釉薬が素地２０の内部に浸透し、浸透層１５が形成される。ここで、素地２０の内部に浸透するのは、主として燐酸アルミニウムである。その後、焼成すると、燐酸アルミニウムと素地とが反応してガラス化し、浸透しなかった釉薬により形成される釉薬層１０自体もガラス化するので、焼成後に形成される釉薬層１０は、素地の表面側の一部、すなわち、浸透層１５を含めた形で形成される。
【００４５】
つまり、本発明の釉薬は、上記化３の釉式におけるＲ₂Ｏ（塩基性物質）と燐酸アルミニウムとを多く含有し、また、素地は、本来、Ｒ₂Ｏ₃（中性物質）とＲＯ₂（酸性物質）を多く含有することから、本発明の釉薬と素地とでいわゆるマトリックスが形成され、釉薬を施釉すると、釉薬、特に、燐酸アルミニウムが素地に浸透して浸透層を形成し、その後焼成することによって施釉層及び浸透層が溶融してガラス化して、結果として釉薬層が厚く形成されるのである。なお、素地の組成や釉薬の浸透度合いによって焼成により形成される釉薬層の厚みや釉調は異なることになる。
【００４６】
よって、本発明の釉薬によれば、素地に浸透して素地の釉薬塗布側の一部も釉薬層に形成するので、極めて少ない量の釉薬で済ますことが可能となる。具体的には、通常の釉薬の使用量に比べて、約２０％の使用量で済ますことができ、約８０％の釉薬の消費を減らすことが可能となる。これにより、製造原料のコスト削減を図ることができ、また、施釉量が少なくて済むので、焼成エネルギーを減少させることができ、また、製造設備を簡素化することができる。また、本発明の釉薬により形成された釉薬層は、素地の一部に浸透した状態で形成されるので、釉薬層が素地層から分離しにくく、釉薬層の貫乳の問題を少なくすることが可能となる。
【００４７】
なお、釉薬の組成は、焼成温度等の条件に応じて調整する。調整のいくつかの具体例が以下の実施例に示される。
【００４８】
次に、具体的な実施例について説明する。まず、第１実施例について説明する。この第１実施例は、１１００℃の焼成温度の場合で、製品としては瓦の場合の例である。
【００４９】
この第１実施例における釉薬は、基礎釉薬と、低溶融フリット（フリット）と、燐酸アルミニウムの３成分により形成されている。
【００５０】
ここで、上記基礎釉薬の材料組成としては、表１に示すように、重量比で、ボールクレーが２７．４％、カオリンが８．１％、ワラストナイトが２４．２％、酸化亜鉛が１６．１％、珪酸ジルコニウムが２４．２％となっている。
【００５１】
【表１】

【００５２】
また、上記基礎釉薬の化学組成としては、表２に示すように、重量比で、ＣａＯが１１．６３％、ＺｎＯが１６．８８％、Ａｌ₂Ｏ₃が１４．０３％、ＳｉＯ₂が４０．４５％、ＺｒＯ₂が１７．０１％となっており、モル比では、ＣａＯが１５．４３％、ＺｎＯが１５．４３％、Ａｌ₂Ｏ₃が９．８８％、ＳｉＯ₂が４９．０７％、ＺｒＯ₂が１０．１９％となっている。つまり、表１の材料組成を化学組成として示すと、表２に示すようになる。
【００５３】
【表２】

【００５４】
また、該基礎釉薬をゼーゲル式としての化学式で示すと、化４に示すようになる。つまり、表１の材料組成や表２の化学組成をゼーゲル式で示すと化４に示すようになる。
【００５５】
【化４】

【００５６】
次に、上記低溶融フリットの化学組成としては、表３に示すように、重量比で、ＳｉＯ₂が３６．２０％、Ａｌ₂Ｏ₃が３．１６％、ＣａＯが１１．６９％、Ｋ₂Ｏが１．７２％、Ｎａ₂Ｏが２０．５９％、Ｂ₂Ｏ₃が２６．６４％となっており、また、モル比で、ＳｉＯ₂が３８．３０％、Ａｌ₂Ｏ₃が２．１３％、ＣａＯが１３．１２％、Ｋ₂Ｏが１．０６％、Ｎａ₂Ｏが２１．２８％、Ｂ₂Ｏ₃が２４．１１％となっている。
【００５７】
【表３】

【００５８】
また、該低溶融フリットをゼーゲル式としての化学式で示すと、化５に示すようになる。つまり、表３の化学組成をゼーゲル式で示すと化５に示すようになる。
【００５９】
【化５】

【００６０】
次に、上記燐酸アルミニウムとしては、メタ燐酸アルミニウム（Ａｌ（ＰＯ₃）₃）を用いた。
【００６１】
上記の基礎釉薬と、低溶融フリットと、燐酸アルミニウムとを混合して釉薬を生成した。つまり、上記の基礎釉薬の粉末と、低溶融フリットの粉末と、燐酸アルミニウムの粉末とを混合して釉薬を生成した。ここで、基礎釉薬と、低溶融フリットと、燐酸アルミニウムの配合割合は、表４に示すように、重量比で、基礎釉薬が６２％、低溶融フリットが２０％、燐酸アルミニウムが１８％とした。
【００６２】
【表４】

【００６３】
なお、このようにして生成された釉薬の化学組成は、表５に示すように、重量比で、ＳｉＯ₂が３３．６８％、Ａｌ₂Ｏ₃が１５．５８％、ＣａＯが１０．２４％、ＺｎＯが１０．７０％、Ｎａ₂Ｏが４．５７％、、Ｋ₂Ｏが０．３６％、Ｂ₂Ｏ₃が５．１７％、ＺｒＯ₂が１０．８０％、Ｐ₂Ｏ₅が８．９０％となり、モル比では、ＳｉＯ₂が４２．１２％、Ａｌ₂Ｏ₃が１１．４９％、ＣａＯが１３．７４％、ＺｎＯが９．９１％、Ｎａ₂Ｏが５．５５％、、Ｋ₂Ｏが０．３０％、Ｂ₂Ｏ₃が５．５５％、ＺｒＯ₂が６．６１％、Ｐ₂Ｏ₅が４．７３％となる。
【００６４】
【表５】

【００６５】
また、釉薬をゼーゲル式としての化学式で示すと、化６に示すようになる。つまり、表５の化学組成をゼーゲル式で示すと化６に示すようになる。
【００６６】
【化６】

【００６７】
そして、この釉薬を水に粉砕分散して液状とした後、釉薬を瓦用せっ器質配土により形成された素地に施釉し、その後、焼成（１１００℃／９０ｍｉｎ Ｓｏａｋｉｎｇ Ｅ．Ｋ）したところ、施釉する面積当たりの通常の使用量に比べて２０％の使用量でも、十分な釉薬層を形成することができた。なお、釉薬における低溶融フリットと燐酸アルミニウムの配合割合を多くすると、釉薬の融点が低下し、釉薬層の透明性が高くなる。一方、釉薬における基礎釉薬の配合割合を多くすると、釉薬の融点が高くなり釉薬層の乳濁性が高くなるという結果になった。
【００６８】
なお、上記の説明では、釉薬における配合割合を、重量比で、基礎釉薬が６２％、低溶融フリットが２０％、燐酸アルミニウムが１８％としたが、表４に示すように、重量比で、基礎釉薬が５０〜７０％、低溶融フリット１０〜３０％、燐酸アルミニウムが１０〜３０％の範囲内とすることが可能である。
【００６９】
次に、第２実施例について説明する。この第２実施例は、酸化雰囲気における１２５０℃の焼成温度の場合で、製品としては、タイルや、衛生陶器等の一般陶磁器製品の場合の例である。
【００７０】
この第２実施例における釉薬は、同様に、基礎釉薬と、低溶融フリット（フリット）と、燐酸アルミニウムとを有している。
【００７１】
ここで、上記基礎釉薬の材料組成としては、表６に示すように、重量比で、長石(Ｋ₂Ｏ系)が１３％、仮焼カオリンが４０％、ボールクレーが５％、珪石が５％、ワラストナイトが１３％、仮焼亜鉛が８％、珪酸ジルコニウムが１６％となっている。
【００７２】
【表６】

【００７３】
また、上記基礎釉薬の化学組成としては、表７に示すように、重量比で、ＳｉＯ₂が５０．５８％で、Ａｌ₂Ｏ₃が２２．３５％で、ＣａＯが６．３０％で、ＺｎＯが８．２３％で、Ｋ₂Ｏが１．０５％で、Ｎａ₂Ｏが０．４１％で、ＺｒＯ₂が１１．０８％となっており、モル比では、ＳｉＯ₂が６０．８３％で、Ａｌ₂Ｏ₃が１５．８０％で、ＣａＯが８．１６％で、ＺｎＯが７．３４％で、Ｋ₂Ｏが６．５３％で、Ｎａ₂Ｏが０．８２％で、ＺｒＯ₂が０．５２％となっている。つまり、表６の材料組成を化学組成として示すと、表７に示すようになる。
【００７４】
【表７】

【００７５】
また、該基礎釉薬をゼーゲル式としての化学式で示すと、化７に示すようになる。つまり、表６の材料組成や表７の化学組成をゼーゲル式で示すと化７に示すようになる。
【００７６】
【化７】

【００７７】
次に、上記低溶融フリットの化学組成としては、表８に示すように、重量比で、ＳｉＯ₂が３６．２０％、Ａｌ₂Ｏ₃が３．１６％、ＣａＯが１１．６９％、Ｋ₂Ｏが１．７２％、Ｎａ₂Ｏが２０．５９％、Ｂ₂Ｏ₃が２６．６４％となっており、また、モル比で、ＳｉＯ₂が３８．３０％、Ａｌ₂Ｏ₃が２．１３％、ＣａＯが１３．１２％、Ｋ₂Ｏが１．０６％、Ｎａ₂Ｏが２１．２８％、Ｂ₂Ｏ₃が２４．１１％となっている。つまり、本実施例の低溶融フリットの化学組成は、上記第１実施例の場合と同様である。
【００７８】
【表８】

【００７９】
また、該低溶融フリットをゼーゲル式としての化学式で示すと、化８に示すようになる。つまり、表８の化学組成をゼーゲル式で示すと化８に示すようになる。
【００８０】
【化８】

【００８１】
次に、上記燐酸アルミニウムとしては、メタ燐酸アルミニウム（Ａｌ（ＰＯ₃）₃）を用いた。
【００８２】
上記の基礎釉薬と、低溶融フリットと、燐酸アルミニウムとを混合して釉薬を生成した。つまり、上記の基礎釉薬の粉末と、低溶融フリットの粉末と、燐酸アルミニウムの粉末とを混合して釉薬を生成した。ここで、基礎釉薬と、低溶融フリットと、燐酸アルミニウムの配合割合は、表９に示すように、重量比で、基礎釉薬が７６％、低溶融フリットが１４％、燐酸アルミニウムが１０％とした。
【００８３】
【表９】

【００８４】
なお、このようにして生成された釉薬の化学組成は、表１０に示すように、重量比で、ＳｉＯ₂が４４．６０％、Ａｌ₂Ｏ₃が２０．９３％、ＣａＯが６．５６％、ＺｎＯが６．３４％、Ｎａ₂Ｏが３．３１％、、Ｋ₂Ｏが１．０６％、Ｂ₂Ｏ₃が３．８９％、ＺｒＯ₂が８．５１％、Ｐ₂Ｏ₅が４．８０％となり、モル比では、ＳｉＯ₂が５４．３９％、Ａｌ₂Ｏ₃が１５．０１％、ＣａＯが８．５６％、ＺｎＯが５．７１％、Ｎａ₂Ｏが３．８８％、、Ｋ₂Ｏが０．８１％、Ｂ₂Ｏ₃が４．１０％、ＺｒＯ₂が５．０５％、Ｐ₂Ｏ₅が２．４９％となる。
【００８５】
【表１０】

【００８６】
また、釉薬をゼーゲル式としての化学式で示すと、化９に示すようになる。つまり、表１０の化学組成をゼーゲル式で示すと化９に示すようになる。
【００８７】
【化９】

【００８８】
そして、この釉薬を水に粉砕分散して液状とした後、釉薬を瓦用磁器質配土により形成された素地に施釉し、その後、焼成（１２５０℃（ＯＦ）／９０ｍｉｎＳｏａｋｉｎｇ Ｅ．Ｋ）したところ、施釉する面積当たりの通常の使用量に比べて２０％の使用量でも、十分な釉薬層を形成することができた。なお、釉薬における低溶融フリットと燐酸アルミニウムの配合割合を多くすると、釉薬の融点が低下し、釉薬層の透明性が高くなる。一方、釉薬における基礎釉薬の配合割合を多くすると、釉薬の融点が高くなり釉薬層の乳濁性が高くなるという結果になった。
【００８９】
なお、上記の説明では、釉薬における配合割合を、重量比で、基礎釉薬が７６％、低溶融フリットが１４％、燐酸アルミニウムが１０％としたが、表９に示すように、重量比で、基礎釉薬が６０〜８０％、低溶融フリット５〜２０％、燐酸アルミニウムが５〜２０％の範囲内とすることが可能である。
【００９０】
次に、第３実施例について説明する。この第３実施例は、特に、乳濁釉の場合の例であり、酸化雰囲気における１２５０℃の焼成温度の場合で、製品としては、タイルや、衛生陶器等の一般陶磁器製品の場合の例である。
【００９１】
この第３実施例における釉薬は、同様に、基礎釉薬と、低溶融フリット（フリット）と、燐酸アルミニウムとを有している。
【００９２】
ここで、上記基礎釉薬の材料組成としては、表１１に示すように、重量比で、長石(Ｎａ系)が１５％、仮焼カオリンが４０％、ボールクレーが５％、珪石が５％、ワラストナイトが１３％、仮焼亜鉛が７％、珪酸ジルコニウムが１５％となっている。
【００９３】
【表１１】

【００９４】
また、上記基礎釉薬の化学組成としては、表１２に示すように、重量比で、ＳｉＯ₂が５２．０９％で、Ａｌ₂Ｏ₃が２２．３４％で、ＣａＯが６．３５％で、ＺｎＯが７．１９％で、Ｋ₂Ｏが１．２１％で、Ｎａ₂Ｏが０．４７％で、ＺｒＯ₂が１０．３５％となっており、モル比では、ＳｉＯ₂が６２．３０％で、Ａｌ₂Ｏ₃が１５．６８％で、ＣａＯが８．１７％で、ＺｎＯが６．３３％で、Ｋ₂Ｏが０．９６％で、Ｎａ₂Ｏが０．５２％で、ＺｒＯ₂が６．０４％となっている。つまり、表１１の材料組成を化学組成として示すと、表１２に示すようになる。
【００９５】
【表１２】

【００９６】
また、該基礎釉薬をゼーゲル式としての化学式で示すと、化１０に示すようになる。つまり、表１１の材料組成や表１２の化学組成をゼーゲル式で示すと化１０に示すようになる。
【００９７】
【化１０】

【００９８】
次に、上記低溶融フリットの化学組成としては、表１３に示すように、重量比で、ＳｉＯ₂が３６．２０％、Ａｌ₂Ｏ₃が３．１６％、ＣａＯが１１．６９％、Ｋ₂Ｏが１．７２％、Ｎａ₂Ｏが２０．５９％、Ｂ₂Ｏ₃が２６．６４％となっており、また、モル比で、ＳｉＯ₂が３８．３０％、Ａｌ₂Ｏ₃が２．１３％、ＣａＯが１３．１２％、Ｋ₂Ｏが１．０６％、Ｎａ₂Ｏが２１．２８％、Ｂ₂Ｏ₃が２４．１１％となっている。つまり、本実施例の低溶融フリットの化学組成は、上記第１実施例及び第２実施例の場合と同様である。
【００９９】
【表１３】

【０１００】
また、該低溶融フリットをゼーゲル式としての化学式で示すと、化１１に示すようになる。つまり、表１３の化学組成をゼーゲル式で示すと化１１に示すようになる。
【０１０１】
【化１１】

【０１０２】
次に、上記燐酸アルミニウムとしては、メタ燐酸アルミニウム（Ａｌ（ＰＯ₃）₃）を用いた。
【０１０３】
上記の基礎釉薬と、低溶融フリットと、燐酸アルミニウムとを混合して釉薬を生成した。つまり、上記の基礎釉薬の粉末と、低溶融フリットの粉末と、燐酸アルミニウムの粉末とを混合して釉薬を生成した。ここで、基礎釉薬と、低溶融フリットと、燐酸アルミニウムの配合割合は、表１４に示すように、重量比で、基礎釉薬が８５％、低溶融フリットが６％、燐酸アルミニウムが９％とした。
【０１０４】
【表１４】

【０１０５】
なお、このようにして生成された釉薬の化学組成は、表１５に示すように、重量比で、ＳｉＯ₂が４７．２３％、Ａｌ₂Ｏ₃が２２．６０％、ＣａＯが６．１７％、ＺｎＯが６．２１％、Ｎａ₂Ｏが１．７０％、、Ｋ₂Ｏが１．１５％、Ｂ₂Ｏ₃が１．６７％、ＺｒＯ₂が８．９４％、Ｐ₂Ｏ₅が４．３３％となり、モル比では、ＳｉＯ₂が５７．７８％、Ａｌ₂Ｏ₃が１６．３０％、ＣａＯが８．０８％、ＺｎＯが５．６５％、Ｎａ₂Ｏが１．９８％、、Ｋ₂Ｏが０．８８％、Ｂ₂Ｏ₃が１．７６％、ＺｒＯ₂が５．３６％、Ｐ₂Ｏ₅が２．２０％となる。
【０１０６】
【表１５】

【０１０７】
また、釉薬をゼーゲル式としての化学式で示すと、化１２に示すようになる。つまり、表１５の化学組成をゼーゲル式で示すと化１２に示すようになる。
【０１０８】
【化１２】

【０１０９】
そして、この釉薬を水に分散して液状とした後、釉薬をタイル用半磁器質配土により形成された素地に施釉し、その後、焼成（１２５０℃／９０ｍｉｎ Ｓｏａｋｉｎｇ Ｅ．Ｋ）したところ、施釉する面積当たりの通常の使用量に比べて２０％の使用量でも、十分な釉薬層を形成することができた。なお、釉薬における低溶融フリットと燐酸アルミニウムの配合割合を多くすると、釉薬の融点が低下し、マット釉（艶消し釉）としての白濁性が低くなる。一方、釉薬における基礎釉薬の配合割合を多くすると、釉薬の融点が高くなり釉薬層の白濁性が高くなるという結果になった。
【０１１０】
なお、上記の説明では、釉薬における配合割合を、重量比で、基礎釉薬が８５％、低溶融フリットが６％、燐酸アルミニウムが９％としたが、表１４に示すように、重量比で、基礎釉薬が７０〜９０％、低溶融フリット５〜２０％、燐酸アルミニウムが５〜２０％の範囲内とすることが可能である。
【０１１１】
次に、第４実施例について説明する。この第４実施例は、低温の焼成温度、具体的には、１０００℃の焼成温度の場合で、製品としては、瓦の場合の例である。
【０１１２】
この第４実施例における釉薬は、同様に、基礎釉薬と、低溶融フリットと、燐酸アルミニウムとを有している。
【０１１３】
ここで、本実施例の釉薬の材料組成について説明すると、表１６に示すように構成され、ボールクレーが１８％、ワラストナイトが１５％、酸化亜鉛が１０％、珪酸ジルコニウムが１５％、硼珪酸フリットが２２％、メタ燐酸アルミニウムが２０％となっている。
【０１１４】
【表１６】

【０１１５】
この表１６に示す材料組成において、ボールクレーと、ワラストナイトと、酸化亜鉛と、珪酸ジルコニウムとが、上記基礎釉薬に相当する。基礎釉薬におけるボールクレーと、ワラストナイトと、酸化亜鉛と、珪酸ジルコニウムの重量比は、表１６に示す基本値の重量比からすると、ボールクレーが３１．０％で、ワラストナイトが２５．９％で、酸化亜鉛が１７．２％で、珪酸ジルコニウムが２５．９％となる。また、硼珪酸フリットが、上記低溶融フリットに相当する。
【０１１６】
また、釉薬の化学組成は、表１７に示すように構成され、重量比で、ＳｉＯ₂が３１．９８％、Ａｌ₂Ｏ₃が１４．６４％、ＣａＯが１０．０３％、ＺｎＯが１０．８２％、Ｎａ₂Ｏが４．９０％、、Ｋ₂Ｏが０．４２％、Ｂ₂Ｏ₃が６．３４％、ＺｒＯ₂が１０．９０％、Ｐ₂Ｏ₅が９．９７％となり、モル比では、ＳｉＯ₂が４０．２６％、Ａｌ₂Ｏ₃が１０．８７％、ＣａＯが１３．５２％、ＺｎＯが１０．１２％、Ｎａ₂Ｏが５．９７％、、Ｋ₂Ｏが０．３８％、Ｂ₂Ｏ₃が６．８７％、ＺｒＯ₂が６．７２％、Ｐ₂Ｏ₅が５．２９％となる。つまり、表１６の材料組成を化学組成として示すと、表１７に示すようになる。
【０１１７】
【表１７】

【０１１８】
また、釉薬をゼーゲル式としての化学式で示すと、化１３に示すようになる。つまり、表１７の化学組成をゼーゲル式で示すと化１３に示すようになる。
【０１１９】
【化１３】

【０１２０】
本実施例の釉薬の製造方法は、上記と同様であり、各材料の粉末を混合して釉薬を生成する。
【０１２１】
そして、この釉薬を水に分散して液状とした後、釉薬を瓦用磁器質配土により形成された素地に施釉し、その後、焼成（１０００℃／６０ｍｉｎ Ｓｏａｋｉｎｇ Ｅ．Ｋ）したところ、施釉する面積当たりの通常の使用量に比べて２０％の使用量でも、十分な釉薬層を形成することができ、乳濁性光沢釉として非常に良好な釉薬であることが判明した。なお、釉薬における低溶融フリットと燐酸アルミニウムの配合割合を多くすると、釉薬の融点が低下し、釉薬層の透明性が高くなる。一方、釉薬における基礎釉薬の配合割合を多くすると、釉薬の融点が高くなり釉薬層の乳濁性が高くなるという結果になった。
【０１２２】
なお、上記の説明では、釉薬における配合割合を、表１６の「基本値」に示す値とするとして説明したが、ボールクレーが１５〜２５％、ワラストナイトが１０〜２５％、酸化亜鉛が５〜１５％、珪酸ジルコニウムが５〜２０％、硼珪酸フリットが１５〜３０％、メタ燐酸アルミニウムが５〜２５％の範囲内とすることが可能である。
【０１２３】
なお、上記の説明において、釉薬には、燐酸アルミニウムを含有するものとして説明したが、これには限られず、燐酸アルミニウム化合物を用いてもよい。この燐酸アルミニウム化合物としては、例えば、燐酸（Ｈ₃ＰＯ₄）と亜燐酸（Ｈ₃ＰＯ₃）と次亜燐酸（Ｈ₃ＰＯ₂）とにおけるいずれかと、酸化アルミニウム（Ａｌ₂Ｏ₃）と水酸化アルミニウム（Ａｌ（ＯＨ）₃ｎＨ₂Ｏ）とにおけるいずれかと、を合成した化合物としてもよい。また、この燐酸アルミニウム化合物としては、燐酸基と、アルミニウム基と、を有するものであってもよい。このような場合にも、施釉した釉薬は素地に浸透し、焼成すると、素地と反応してガラス化することになる。なお、該燐酸基は、メタ燐酸基をも含む意味である。
【０１２４】
また、上記の説明において、釉薬は、基礎釉薬と、低溶融フリットと、燐酸アルミニウムとを有するものとして説明したが、これらにさらに、金属酸化物を加えて着色した釉薬としてもよい。また、基礎釉薬と、低溶融フリットと、燐酸アルミニウムにさらに、無機顔料を加えて着色した釉薬としてもよい。
【０１２５】
また、上記各実施例において釉薬の釉式を化６、化９、化１２、化１３に示すように説明したが、これには限られず、以下の化１４に示す範囲の釉式（ゼーゲル式）を持つ釉薬であればよい。
【０１２６】
【化１４】

【０１２７】
ただし、上記化１４において、Ｘ＝０．３０〜０．６０、Ｙ＝０．２５〜０．４０、Ｚ＝０．０５〜０．２５、Ｗ＝０．０１〜０．１０、Ｘ＋Ｙ＋Ｚ＋Ｗ＝１である。
【０１２８】
なお、上記の説明においては、窯業製品として上記各製品を例に取って説明したが、それらの各製品以外の窯業製品であってもよい。
【０１２９】
【発明の効果】
本発明に基づく釉薬及び瓦によれば、燐酸アルミニウムを含有する等の構成となっているので、釉薬が素地に浸透して素地の釉薬塗布側の一部も釉薬層に形成するので、極めて少ない量の釉薬で済ますことが可能となり、これにより、製造原料のコスト削減を図ることができ、また、施釉量が少なくて済むので、焼成エネルギーを減少させることができ、また、製造設備を簡素化することができる。また、本発明の釉薬により形成された釉薬層は、素地の一部に浸透した状態で形成されるので、釉薬層が素地層から分離しにくく、釉薬層の貫乳の問題を少なくすることが可能となる。また、フリットが含有されているので、釉薬の融点を調整することができる。
【図面の簡単な説明】
【図１】本発明の釉薬を素地に施釉し焼成する場合の状態を説明するための説明図であり、（ａ）は施釉直後の状態を示す説明図であり、（ｂ）は施釉後所定時間経過後の状態を示す説明図であり、（ｃ）は焼成後の状態を示す説明図である。
【図２】従来における釉薬を素地に施釉し焼成する場合の状態を説明するための説明図であり、（ａ）は施釉後の状態を示す説明図であり、（ｂ）は焼成後の状態を示す説明図である。
【符号の説明】
１０、１０’ 釉薬層
１５ 浸透層
２０ 素地[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a glaze for ceramics, and to a glaze used for ceramic products.
[0002]
[Prior art]
Conventionally, the glaze is solidified by applying the glaze to the surface of the substrate and then firing, whereby a glaze layer is formed on the surface of the substrate. This glaze layer is independent of the substrate layer. That is, as a bonded state after firing, the base layer and the glaze layer are composed of components different in chemical formula.
[0003]
The applicant has not searched prior art documents, and there is no prior art document to be described.
[0004]
[Problems to be solved by the invention]
However, since the glaze layer and the base layer are independent as described above, there is a problem that a large amount of glaze is required. In other words, the glaze layer, in addition to providing decorative properties for ceramic products, eliminates the permeability of liquids and gases, makes the surface smooth and less soiled, and increases the physical or chemical strength of ceramic products. However, since the glaze layer and the base layer are independent of each other, a certain amount of glaze is required to achieve the above-mentioned purpose.
[0005]
In addition, since the glaze layer and the base layer are independent, the glaze layer may be easily separated from the base layer, causing problems such as milk penetration of the glaze layer. That is, when the glaze is applied to the substrate 20, the glaze layer 10 ′ is formed by the glaze (see FIG. 2A), and even if this is fired, the glaze layer 10 ′ is formed on the surface of the substrate 20. And are formed separately (see FIG. 2B).
[0006]
Therefore, it is possible to significantly reduce the amount of glaze used by infiltrating the glaze into the substrate, thereby reducing the cost of manufacturing raw materials, reducing the burning energy, and thus simplifying the manufacturing equipment. In addition, the glaze layer formed by baking is difficult to separate from the base layer, and the object is to provide a glaze with less problems of milk penetration of the glaze layer.
[0007]
[Means for Solving the Problems]
  The present invention was created to solve the above problems, and firstly,Used for roof tilesA glaze,A basic glaze containing ball clay, kaolin, wollastonite, zinc oxide, and zirconium silicate. A frit composed of a borosilicate frit as a component frit, and a frit having a blending ratio in the glaze of 10 to 30% by weight, and a first aluminum phosphate (Al (H ₂ PO _Four ) _Three ) And dibasic aluminum phosphate (Al ₂ (HPO _Four ) _Three ) And aluminum metaphosphate (Al (PO _Three ) _Three ) And at least one of aluminum phosphate, and the blending ratio in the glaze is 10 to 30% by weightAluminum phosphateWhen,And having a permeability to the substrate to which the glaze is applied by aluminum phosphate.
[0009]
  According to the glaze of this first composition, it contains aluminum phosphate, so the glaze penetrates into the base and part of the glaze application side of the base also forms in the glaze layer, so an extremely small amount of glaze can be used As a result, it is possible to reduce the cost of manufacturing raw materials and to reduce the amount of glazing, so that the firing energy can be reduced and the manufacturing equipment can be simplified. In addition, since the glaze layer formed by the glaze of the present invention is formed in a state of penetrating a part of the substrate, the glaze layer is difficult to separate from the substrate layer, and the problem of milk penetration of the glaze layer may be reduced. It becomes possible.Moreover, since the frit is contained, the melting point of the glaze can be adjusted.
[0032]
  Secondly,tileAnd it is manufactured by applying the glaze of said 1st structure and baking it.
[0033]
  Of this second configurationtileAccording to the above釉Since it is manufactured by baking after applying the medicine, the glaze penetrates into the base and part of the base on which the glaze is applied also forms in the glaze layer, so it is possible to use an extremely small amount of glaze Thus, the cost of manufacturing raw materials can be reduced, and the amount of glazing can be reduced, so that the firing energy can be reduced and the manufacturing equipment can be simplified. In addition, since the glaze layer formed by the glaze of the present invention is formed in a state of penetrating a part of the substrate, the glaze layer is difficult to separate from the substrate layer, and the problem of milk penetration of the glaze layer may be reduced. It becomes possible. Moreover, since the frit is contained, the melting point of the glaze can be adjusted.
[0034]
DETAILED DESCRIPTION OF THE INVENTION
Embodiments of the present invention will be described with reference to the drawings. The glaze according to the present invention is composed of a basic glaze, a low melting frit (frit), and aluminum phosphate.
[0035]
Here, the basic glaze is used to maintain the volume feeling of the fired product as a bowl, to increase the chemical or physical strength of the surface, and to obtain emulsion. As this basic glaze, conventional basic glazes can be applied. For example, raw ores, metal oxides, carbonates and the like are contained, but the glaze of the present invention contains aluminum phosphate. The ratio of the composition having a high melting temperature is set higher than usual, and the ratio of the composition having a strong emulsion is increased. The basic glaze contains a large amount of free silica. This is because single crystal silicic acid (SiO₂This is because bubbles are generated during firing, and aluminum phosphate and silicic acid (SiO₂This is because the reaction is carried out at a high temperature.
[0036]
The low melting frit is a borosilicate frit, that is, a frit mainly composed of boric acid and silicon dioxide. This low melting frit is used to lower the melting point of the glaze and increase the surface gloss of ceramic products.
[0037]
The aluminum phosphate includes a first aluminum phosphate (Al (H₂PO_Four)_Three), Dibasic aluminum phosphate (Al₂(HPO_Four)_Three), Aluminum metaphosphate (Al (PO_Three)_ThreeAny of these aluminum phosphates can be applied, but in the glaze of the present invention, aluminum metaphosphate (Al (PO_Three)_Three) Is particularly preferred.
[0038]
Here, as a blending ratio of the basic glaze, the low melting frit, and the aluminum phosphate, the basic glaze is 20 to 90%, the low melting frit is 0 to 40%, and the aluminum phosphate is 5 to 50% by weight. It is preferable to do this. More preferably, the basic glaze is 50 to 70%, the low melting frit is 10 to 20%, and the aluminum phosphate is 5 to 30% by weight.
[0039]
In general, the basic formula of the glaze is shown as shown in the following chemical formula 3.
[0040]
[Chemical 3]

[0041]
And as the glaze of this invention, R₂It is configured to contain a large amount of O (basic substance) and aluminum phosphate.
[0042]
The glaze is produced by mixing the basic glaze powder, the low melting frit powder, and the aluminum phosphate powder.
[0043]
As a method of using the glaze of the present invention, the glaze is pulverized and dispersed in water and applied to the substrate as a liquid, and then fired in the same manner as a normal glaze. In this way, ceramic products are manufactured. Since the glaze of the present invention contains aluminum phosphate, it has excellent permeability, and when the glaze is applied to the substrate, the glaze penetrates into the substrate. After that, the glaze and substrate are baked and hardened. That is, the glaze that has penetrated into the substrate and the component of the substrate react to be baked and hardened. Thereby, the glaze layer formed with the glaze of this invention will be in the state which osmose | permeated to some base materials.
[0044]
That is, if it demonstrates using drawing, if the glaze of this invention is applied to the base 20, the glaze layer 10 will be formed in the base 20 (refer Fig.1 (a)). Then, after the glazing, as shown in FIG. 1 (b), the glaze penetrates into the substrate 20, and the permeation layer 15 is formed. Here, it is mainly aluminum phosphate that penetrates into the substrate 20. Thereafter, when fired, the aluminum phosphate and the base react to vitrify, and the glaze layer 10 itself formed by the glaze that has not permeated also vitrifies. Therefore, the glaze layer 10 formed after firing is formed on the surface side of the base. That is, a part including the osmotic layer 15 is formed.
[0045]
That is, the glaze of the present invention is R in the formula 3₂It contains a large amount of O (basic substance) and aluminum phosphate, and the substrate is essentially R₂O_Three(Neutral substances) and RO₂Since it contains a large amount of (acidic substance), a so-called matrix is formed with the glaze of the present invention and the base, and when the glaze is applied, the glaze, particularly aluminum phosphate, penetrates the base to form a permeation layer, and then fired. By doing so, the glaze layer and the permeation layer are melted and vitrified, and as a result, the glaze layer is formed thick. Note that the thickness and tone of the glaze layer formed by firing differ depending on the composition of the substrate and the degree of penetration of the glaze.
[0046]
Therefore, according to the glaze of the present invention, a part of the base on the glaze application side is formed in the glaze layer, so that an extremely small amount of glaze can be used. Specifically, the amount of the glaze can be reduced by about 20% compared with the amount of the normal glaze, and the consumption of the glaze by about 80% can be reduced. Thereby, the cost of manufacturing raw materials can be reduced, and since the amount of glazing can be reduced, the firing energy can be reduced, and the manufacturing equipment can be simplified. In addition, since the glaze layer formed by the glaze of the present invention is formed in a state of penetrating a part of the substrate, the glaze layer is difficult to separate from the substrate layer, and the problem of milk penetration of the glaze layer may be reduced. It becomes possible.
[0047]
The composition of the glaze is adjusted according to conditions such as the firing temperature. Some specific examples of adjustments are shown in the following examples.
[0048]
Next, specific examples will be described. First, the first embodiment will be described. This 1st Example is an example in the case of a calcination temperature of 1100 degreeC, and a tile as a product.
[0049]
The glaze in the first embodiment is formed by three components of a basic glaze, a low melting frit (frit), and aluminum phosphate.
[0050]
Here, as shown in Table 1, the material composition of the basic glaze is 27.4% in ball clay, 8.1% in kaolin, 24.2% in wollastonite, and zinc oxide in weight ratio. 16.1% and zirconium silicate account for 24.2%.
[0051]
[Table 1]

[0052]
In addition, as shown in Table 2, the chemical composition of the basic glaze was 11.63% CaO, 16.88% ZnO, Al, as shown in Table 2.₂O_ThreeIs 14.03%, SiO₂Is 40.45%, ZrO₂Is 17.01%, and by molar ratio, CaO is 15.43%, ZnO is 15.43%, Al₂O_Three9.88%, SiO₂49.07%, ZrO₂Is 10.19%. That is, when the material composition of Table 1 is shown as a chemical composition, it becomes as shown in Table 2.
[0053]
[Table 2]

[0054]
In addition, when the basic glaze is represented by a chemical formula as a Zegel formula, it is as shown in Chemical formula 4. That is, when the material composition shown in Table 1 and the chemical composition shown in Table 2 are shown by the Zegel formula, they are shown in Chemical Formula 4.
[0055]
[Formula 4]

[0056]
Next, as the chemical composition of the low melting frit, as shown in Table 3, the weight ratio is SiO 2.₂36.20%, Al₂O_Three3.16%, CaO 11.69%, K₂O is 1.72%, Na₂O is 20.59%, B₂O_ThreeIs 26.64%, and the molar ratio is SiO.₂Is 38.30%, Al₂O_ThreeIs 2.13%, CaO is 13.12%, K₂O is 1.06%, Na₂O is 21.28%, B₂O_ThreeIs 24.11%.
[0057]
[Table 3]

[0058]
Further, when the low melting frit is represented by a chemical formula as a Seegel formula, it is as shown in Chemical Formula 5. That is, when the chemical composition of Table 3 is represented by the Zegel formula, it is as shown in Chemical Formula 5.
[0059]
[Chemical formula 5]

[0060]
Next, as the aluminum phosphate, aluminum metaphosphate (Al (PO_Three)_Three) Was used.
[0061]
A glaze was produced by mixing the basic glaze described above, a low melting frit and aluminum phosphate. That is, a glaze was produced by mixing the above basic glaze powder, low melting frit powder, and aluminum phosphate powder. Here, as shown in Table 4, the blending ratio of the basic glaze, the low melting frit and the aluminum phosphate was 62% for the basic glaze, 20% for the low melting frit, and 18% for the aluminum phosphate. .
[0062]
[Table 4]

[0063]
In addition, the chemical composition of the glaze thus produced has a weight ratio of SiO 2 as shown in Table 5.₂33.68%, Al₂O_ThreeIs 15.58%, CaO is 10.24%, ZnO is 10.70%, Na₂O is 4.57%, K₂O is 0.36%, B₂O_Three5.17%, ZrO₂Is 10.80%, P₂O_FiveIs 8.90%, and the molar ratio is SiO₂Is 42.12%, Al₂O_ThreeIs 11.49%, CaO is 13.74%, ZnO is 9.91%, Na₂O is 5.55%, K₂O is 0.30%, B₂O_ThreeIs 5.55%, ZrO₂Is 6.61%, P₂O_FiveIs 4.73%.
[0064]
[Table 5]

[0065]
Further, when the glaze is represented by a chemical formula as the Zegel formula, it is as shown in Chemical formula 6. That is, when the chemical composition of Table 5 is represented by the Zegel formula, it is as shown in Chemical formula 6.
[0066]
[Chemical 6]

[0067]
The glaze was pulverized and dispersed in water to form a liquid, and then the glaze was applied to the base formed by the tile-like earthenware tile, and then fired (1100 ° C./90 min Soaking EK). A sufficient glaze layer could be formed even with a usage amount of 20% compared to the normal usage amount per area. Note that when the blending ratio of the low melting frit and aluminum phosphate in the glaze is increased, the melting point of the glaze is lowered and the transparency of the glaze layer is increased. On the other hand, when the blending ratio of the basic glaze in the glaze was increased, the melting point of the glaze was increased and the emulsion of the glaze layer was increased.
[0068]
In the above description, the blending ratio in the glaze was 62% for the basic glaze, 20% for the low melting frit and 18% for the aluminum phosphate, but as shown in Table 4, The basic glaze can be 50 to 70%, the low melting frit 10 to 30%, and the aluminum phosphate 10 to 30%.
[0069]
Next, a second embodiment will be described. The second embodiment is an example in the case of a firing temperature of 1250 ° C. in an oxidizing atmosphere, and the product is a tile or a general ceramic product such as sanitary ware.
[0070]
The glaze in the second embodiment similarly has a basic glaze, a low melting frit (frit), and aluminum phosphate.
[0071]
Here, as the material composition of the basic glaze, as shown in Table 6, feldspar (K₂O-based) is 13%, calcined kaolin is 40%, ball clay is 5%, silica is 5%, wollastonite is 13%, calcined zinc is 8%, and zirconium silicate is 16%.
[0072]
[Table 6]

[0073]
In addition, as the chemical composition of the basic glaze, as shown in Table 7, by weight ratio, SiO₂Is 50.58%, Al₂O_ThreeIs 22.35%, CaO is 6.30%, ZnO is 8.23%, K₂O is 1.05%, Na₂O is 0.41%, ZrO₂Is 11.08%, and the molar ratio is SiO.₂Is 60.83%, Al₂O_ThreeIs 15.80%, CaO is 8.16%, ZnO is 7.34%, K₂O is 6.53%, Na₂O is 0.82% and ZrO₂Is 0.52%. That is, when the material composition of Table 6 is shown as a chemical composition, it becomes as shown in Table 7.
[0074]
[Table 7]

[0075]
Further, when the basic glaze is represented by a chemical formula as a Zegel formula, it is as shown in Chemical formula 7. That is, when the material composition of Table 6 and the chemical composition of Table 7 are shown by the Zegel formula, they are shown in Chemical formula 7.
[0076]
[Chemical 7]

[0077]
Next, as the chemical composition of the low melting frit, as shown in Table 8, the weight ratio is SiO 2.₂36.20%, Al₂O_Three3.16%, CaO 11.69%, K₂O is 1.72%, Na₂O is 20.59%, B₂O_ThreeIs 26.64%, and the molar ratio is SiO.₂Is 38.30%, Al₂O_ThreeIs 2.13%, CaO is 13.12%, K₂O is 1.06%, Na₂O is 21.28%, B₂O_ThreeIs 24.11%. That is, the chemical composition of the low melting frit of the present embodiment is the same as that of the first embodiment.
[0078]
[Table 8]

[0079]
Further, when the low melting frit is represented by a chemical formula as a Seegel formula, it is as shown in Chemical Formula 8. That is, when the chemical composition of Table 8 is represented by the Zegel formula, it is as shown in Chemical Formula 8.
[0080]
[Chemical 8]

[0081]
Next, as the aluminum phosphate, aluminum metaphosphate (Al (PO_Three)_Three) Was used.
[0082]
A glaze was produced by mixing the basic glaze described above, a low melting frit and aluminum phosphate. That is, a glaze was produced by mixing the above basic glaze powder, low melting frit powder, and aluminum phosphate powder. Here, as shown in Table 9, the blending ratio of the basic glaze, the low melting frit, and the aluminum phosphate was 76% for the basic glaze, 14% for the low melting frit, and 10% for the aluminum phosphate. .
[0083]
[Table 9]

[0084]
In addition, the chemical composition of the glaze thus produced has a weight ratio of SiO 2 as shown in Table 10.₂Is 44.60%, Al₂O_ThreeIs 20.93%, CaO is 6.56%, ZnO is 6.34%, Na₂O is 3.31%, K₂O is 1.06%, B₂O_Three3.89%, ZrO₂Is 8.51%, P₂O_FiveIs 4.80%, and the molar ratio is SiO₂Is 54.39%, Al₂O_ThreeIs 15.01%, CaO is 8.56%, ZnO is 5.71%, Na₂O is 3.88%, K₂O is 0.81%, B₂O_Three4.10%, ZrO₂Is 5.05%, P₂O_FiveIs 2.49%.
[0085]
[Table 10]

[0086]
Further, when the glaze is represented by a chemical formula as a Zegel formula, it is as shown in Chemical formula 9. That is, when the chemical composition of Table 10 is represented by the Zegel formula, it is as shown in Chemical formula 9.
[0087]
[Chemical 9]

[0088]
After this glaze was pulverized and dispersed in water to form a liquid, the glaze was applied to the base formed by the tile porcelain distribution, and then fired (1250 ° C. (OF) / 90 min Soaking E.K). A sufficient glaze layer could be formed even with a usage amount of 20% compared to the normal usage amount per area to be glazed. Note that when the blending ratio of the low melting frit and aluminum phosphate in the glaze is increased, the melting point of the glaze is lowered and the transparency of the glaze layer is increased. On the other hand, when the blending ratio of the basic glaze in the glaze was increased, the melting point of the glaze was increased and the emulsion of the glaze layer was increased.
[0089]
In the above description, the blending ratio in the glaze was 76% for the basic glaze, 14% for the low melting frit and 10% for the aluminum phosphate, but as shown in Table 9, The basic glaze can be 60 to 80%, the low melting frit 5 to 20%, and the aluminum phosphate 5 to 20%.
[0090]
Next, a third embodiment will be described. This third embodiment is an example particularly in the case of an emulsion, in the case of a firing temperature of 1250 ° C. in an oxidizing atmosphere, and as an example in the case of a general ceramic product such as a tile or sanitary ware. is there.
[0091]
The glaze in the third embodiment similarly has a basic glaze, a low melting frit (frit), and aluminum phosphate.
[0092]
Here, as the material composition of the basic glaze, as shown in Table 11, feldspar (Na-based) is 15%, calcined kaolin is 40%, ball clay is 5%, silica is 5%, as shown in Table 11. Wollastonite is 13%, calcined zinc is 7%, and zirconium silicate is 15%.
[0093]
[Table 11]

[0094]
In addition, as the chemical composition of the basic glaze, as shown in Table 12, by weight ratio, SiO 2₂Is 52.09%, Al₂O_ThreeIs 22.34%, CaO is 6.35%, ZnO is 7.19%, K₂O is 1.21%, Na₂O is 0.47%, ZrO₂Is 10.35%, and the molar ratio is SiO₂Is 62.30%, Al₂O_ThreeIs 15.68%, CaO is 8.17%, ZnO is 6.33%, K₂O is 0.96%, Na₂O is 0.52% and ZrO₂Is 6.04%. That is, when the material composition of Table 11 is shown as a chemical composition, it becomes as shown in Table 12.
[0095]
[Table 12]

[0096]
Further, when the basic glaze is represented by a chemical formula as a Zegel formula, it is as shown in Chemical formula 10. That is, when the material composition of Table 11 and the chemical composition of Table 12 are shown by the Zegel formula, they are shown in Chemical formula 10.
[0097]
[Chemical Formula 10]

[0098]
Next, as the chemical composition of the low melting frit, as shown in Table 13, the weight ratio is SiO 2.₂36.20%, Al₂O_Three3.16%, CaO 11.69%, K₂O is 1.72%, Na₂O is 20.59%, B₂O_ThreeIs 26.64%, and the molar ratio is SiO.₂Is 38.30%, Al₂O_ThreeIs 2.13%, CaO is 13.12%, K₂O is 1.06%, Na₂O is 21.28%, B₂O_ThreeIs 24.11%. That is, the chemical composition of the low melting frit of the present example is the same as that of the first and second examples.
[0099]
[Table 13]

[0100]
Further, when the low melting frit is represented by a chemical formula as a Seegel formula, it is as shown in Chemical Formula 11. That is, when the chemical composition of Table 13 is represented by the Zegel formula, it is as shown in Chemical Formula 11.
[0101]
Embedded image

[0102]
Next, as the aluminum phosphate, aluminum metaphosphate (Al (PO_Three)_Three) Was used.
[0103]
A glaze was produced by mixing the basic glaze described above, a low melting frit and aluminum phosphate. That is, a glaze was produced by mixing the above basic glaze powder, low melting frit powder, and aluminum phosphate powder. Here, as shown in Table 14, the blending ratio of the basic glaze, the low melting frit, and the aluminum phosphate was 85% for the basic glaze, 6% for the low melting frit, and 9% for the aluminum phosphate. .
[0104]
[Table 14]

[0105]
In addition, the chemical composition of the glaze thus produced has a weight ratio of SiO 2 as shown in Table 15.₂Is 47.23%, Al₂O_ThreeIs 22.60%, CaO is 6.17%, ZnO is 6.21%, Na₂O is 1.70%, K₂O is 1.15%, B₂O_Three1.67%, ZrO₂Is 8.94%, P₂O_FiveIs 4.33%, and the molar ratio is SiO.₂Is 57.78%, Al₂O_ThreeIs 16.30%, CaO is 8.08%, ZnO is 5.65%, Na₂O is 1.98%, K₂O is 0.88%, B₂O_ThreeIs 1.76%, ZrO₂Is 5.36%, P₂O_FiveIs 2.20%.
[0106]
[Table 15]

[0107]
Further, when the glaze is represented by a chemical formula as the Zegel formula, it is as shown in Chemical formula 12. That is, when the chemical composition of Table 15 is represented by the Zegel formula, it is as shown in Chemical formula 12.
[0108]
Embedded image

[0109]
And after disperse | distributing this glaze to water and making it liquefied, when glaze was applied to the base | substrate formed with the semi-porcelain distribution for tiles, and it fired (1250 degreeC / 90min Soaking EK) after that, A sufficient glaze layer could be formed even with a usage amount of 20% compared to the normal usage amount per area. If the blending ratio of the low melting frit and aluminum phosphate in the glaze is increased, the melting point of the glaze is lowered and the white turbidity as a matte (matte wrinkle) is lowered. On the other hand, when the blending ratio of the basic glaze in the glaze was increased, the melting point of the glaze was increased and the cloudiness of the glaze layer was increased.
[0110]
In the above description, the blending ratio in the glaze was 85% for the basic glaze, 6% for the low melting frit and 9% for the aluminum phosphate, but as shown in Table 14, It is possible to make the basic glaze within the range of 70 to 90%, the low melting frit 5 to 20%, and the aluminum phosphate 5 to 20%.
[0111]
Next, a fourth embodiment will be described. The fourth embodiment is an example in the case of a low firing temperature, specifically, a firing temperature of 1000 ° C., and the product is a roof tile.
[0112]
The glaze in the fourth embodiment similarly has a basic glaze, a low melting frit, and aluminum phosphate.
[0113]
Here, the material composition of the glaze of this example will be described as shown in Table 16. The composition is as shown in Table 16, ball clay is 18%, wollastonite is 15%, zinc oxide is 10%, zirconium silicate is 15%, boron Silica frit is 22% and aluminum metaphosphate is 20%.
[0114]
[Table 16]

[0115]
  In the material composition shown in Table 16, ball clay, wollastonite, zinc oxide, and zirconium silicate correspond to the basic glaze. The weight ratio of ball clay, wollastonite, zinc oxide, and zirconium silicate in the basic glaze is 31.0% for ball clay and 25.wollastonite based on the weight ratio of the basic values shown in Table 16. 9%, zinc oxide 17.2% and zirconium silicate 25.9%. Borosilicate frit is equivalent to the above low melting fritTo do.
[0116]
Moreover, the chemical composition of the glaze is configured as shown in Table 17, and the weight ratio is SiO.₂Is 31.98%, Al₂O_ThreeIs 14.64%, CaO is 10.03%, ZnO is 10.82%, Na₂4.90% for O, K₂O is 0.42%, B₂O_ThreeIs 6.34%, ZrO₂10.90%, P₂O_FiveIs 9.97%, and the molar ratio is SiO₂Is 40.26%, Al₂O_ThreeIs 10.87%, CaO is 13.52%, ZnO is 10.12%, Na₂O is 5.97%, K₂O is 0.38%, B₂O_Three6.87%, ZrO₂6.72%, P₂O_FiveIs 5.29%. That is, when the material composition of Table 16 is shown as a chemical composition, it is as shown in Table 17.
[0117]
[Table 17]

[0118]
Further, when the glaze is represented by the chemical formula as the Zegel formula, it is as shown in Chemical formula 13. In other words, the chemical composition of Table 17 is represented by the chemical formula 13 in terms of the Zegel formula.
[0119]
Embedded image

[0120]
The manufacturing method of the glaze of a present Example is the same as the above, and mixes the powder of each material and produces | generates a glaze.
[0121]
And after disperse | distributing this glaze to water and making it liquid, a glaze is glazed on the base | substrate formed with the porcelain distribution for tiles, and after that, it baked (1000 degreeC / 60min Soaking E.K), and glazed. Even when the amount used was 20% of the normal amount used per area, a sufficient glaze layer could be formed, which proved to be a very good glaze as an emulsion luster. Note that when the blending ratio of the low melting frit and aluminum phosphate in the glaze is increased, the melting point of the glaze is lowered and the transparency of the glaze layer is increased. On the other hand, when the blending ratio of the basic glaze in the glaze was increased, the melting point of the glaze was increased and the emulsion of the glaze layer was increased.
[0122]
In the above description, the blending ratio in the glaze was described as the value shown in “Basic values” in Table 16, but 15-25% for ball clay, 10-25% for wollastonite, and zinc oxide 5-15%, zirconium silicate 5-20%, borosilicate frit 15-30% and aluminum metaphosphate 5-25%.
[0123]
  In the above description, the glaze has been described as containing aluminum phosphate. However, the present invention is not limited to this, and aluminum phosphateConversionA compound may be used. This aluminum phosphateConversionExamples of the compound include phosphoric acid (H_ThreePO_Four) And phosphorous acid (H_ThreePO_Three) And hypophosphorous acid (H_ThreePO₂) And aluminum oxide (Al₂O_Three) And aluminum hydroxide (Al (OH)_ThreenH₂O) and any one ofCompoundIt is good. Also this aluminum phosphateConversionThe compound may have a phosphoric acid group and an aluminum group. Even in such a case, the glaze glaze penetrates into the substrate, and when fired, it reacts with the substrate to be vitrified. The phosphoric acid group also includes a metaphosphoric acid group.
[0124]
In the above description, the glaze has been described as having a basic glaze, a low melting frit, and aluminum phosphate. However, it may be a glaze colored by adding a metal oxide to these. Moreover, it is good also as a glaze colored by adding an inorganic pigment to the basic glaze, the low melting frit, and the aluminum phosphate.
[0125]
In addition, although the formula of the glaze has been described as shown in Chemical Formula 6, Chemical Formula 9, Chemical Formula 12, and Chemical Formula 13 in each of the above-described embodiments, the formula is not limited to this, and the formula shown in the following chemical formula 14 (Seegel formula) ) Any glaze that has
[0126]
Embedded image

[0127]
However, in the above formula 14, X = 0.30-0.60, Y = 0.25-0.40, Z = 0.05-0.25, W = 0.01-0.10, X + Y + Z + W = 1 It is.
[0128]
In the above description, each of the above products has been described as an example of a ceramic product, but ceramic products other than those products may be used.
[0129]
【The invention's effect】
  Glaze according to the invention andtileAccording to the composition of aluminum phosphate, etc., the glaze penetrates into the base and part of the base on the glaze application side also forms in the glaze layer, so an extremely small amount of glaze can be used This makes it possible to reduce the cost of manufacturing raw materials, and since the amount of glazing can be reduced, the firing energy can be reduced and the manufacturing equipment can be simplified. In addition, since the glaze layer formed by the glaze of the present invention is formed in a state of penetrating a part of the substrate, the glaze layer is difficult to separate from the substrate layer, and the problem of milk penetration of the glaze layer may be reduced. It becomes possible. Moreover, since the frit is contained, the melting point of the glaze can be adjusted.
[Brief description of the drawings]
BRIEF DESCRIPTION OF DRAWINGS FIG. 1 is an explanatory diagram for explaining a state in which the glaze of the present invention is applied to a substrate and fired, (a) is an explanatory view showing a state immediately after glazing, and (b) is a predetermined state after glazing. It is explanatory drawing which shows the state after time progress, (c) is explanatory drawing which shows the state after baking.
FIG. 2 is an explanatory view for explaining a state in the case where a glaze is conventionally applied to the substrate and fired, (a) is an explanatory view showing a state after glazing, and (b) is a state after firing. It is explanatory drawing which shows.
[Explanation of symbols]
10, 10 'glaze layer
15 Penetration layer
20 base

Claims (2)

A glaze used for roof tiles,
A basic glaze comprising ball clay, kaolin, wollastonite, zinc oxide, and zirconium silicate, and the blending ratio in the glaze is 50 to 70% by weight,
A frit composed of borosilicate frit, which is a frit mainly composed of boric acid and silicic acid, wherein the blending ratio in the glaze is 10 to 30% by weight,
Phosphoric acid comprising at least one of first aluminum phosphate (Al (H ₂ PO ₄ ) ₃ ), second aluminum phosphate (Al ₂ (HPO ₄ ) ₃ ), and aluminum metaphosphate (Al (PO ₃ ) ₃ ) Aluminum, the proportion of the mixture in the glaze is 10-30% by weight, aluminum phosphate,
Containing
A glaze characterized in that it has a permeability to the substrate on which the glaze is applied by aluminum phosphate. A tile, tile, characterized in that those prepared by calcining after glazed glaze described in claim 1.

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