JP4284403B2 - A method of firing ceramics with lead-free paint containing Cr2O3 - Google Patents

A method of firing ceramics with lead-free paint containing Cr2O3 Download PDF

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JP4284403B2
JP4284403B2 JP02017699A JP2017699A JP4284403B2 JP 4284403 B2 JP4284403 B2 JP 4284403B2 JP 02017699 A JP02017699 A JP 02017699A JP 2017699 A JP2017699 A JP 2017699A JP 4284403 B2 JP4284403 B2 JP 4284403B2
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JP2000219581A (en
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靖雄 芝崎
博道 林
廣 法月
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National Institute of Advanced Industrial Science and Technology AIST
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    • 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
    • C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
    • 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
    • C04B41/5025—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 ceramic materials
    • C04B41/5033—Chromium oxide
    • 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
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/10—Compositions or ingredients thereof characterised by the absence or the very low content of a specific material
    • 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
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/80—Optical properties, e.g. transparency or reflexibility
    • C04B2111/82—Coloured materials

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  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
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  • Inorganic Chemistry (AREA)
  • Glass Compositions (AREA)

Description

【０００１】
【発明の属する技術分野】
本発明は、無鉛絵具の絵付焼成方法に関し、より詳細には、無鉛絵具により装飾を施した陶磁器を絵付焼成する方法に関する。
【０００２】
【従来の技術】
陶磁器類の加飾に用いられる絵具として、有鉛絵具（含鉛絵具）と無鉛絵具がある。有鉛絵具は焼成炉を選ばず、良好な発色・艶を得ることができるが、陶磁器食器からの鉛溶出量規制が強化され、有鉛絵具から無鉛絵具への移行が進められている。
【０００３】
無鉛絵具に関する先行技術は、陶磁器用上絵具及びその製造方法を開示する特公平５−５３７３５号公報に記載されている。前記公報には、二酸化珪素、アルミナ、酸化硼素、アルカリ金属酸化物からなり、希土類元素酸化物、酸化ハフニウム、元素周期表ＶＢ族元素酸化物の１種又は２種以上を含むフリットに、顔料として炭酸銅、酸化第２鉄、３酸化アンチモン、酸化コバルトを混合してなる無鉛の陶磁器用上絵具について記載されており、その効果としては従来の有鉛上絵具に匹敵する旨が記載されている。
【０００４】
従来、無鉛絵具としてＣｒ2Ｏ3を含む無鉛絵具があり、この無鉛絵具で加飾された陶磁器類に関して、電気炉やマッフル炉等の間接加熱型の焼成炉で絵付焼成したものは良好な艶が得られている。
【０００５】
【発明が解決しようとする課題】
しかし、電気炉やマッフル炉等の間接加熱型の焼成炉で焼成することは、生産効率が悪いと共にエネルギー効率も悪い。一方、生産効率とエネルギー効率がより優れたローラーハースキルン等の直接加熱型の焼成炉で、Ｃｒ2Ｏ3を含む無鉛絵具で加飾された陶磁器類の絵付焼成を行う場合には、焼成後の絵具の表面に凹凸が生じ十分な艶を得ることができない、という問題点があった。
【０００６】
本発明の目的は、上記従来技術の問題点を解決し、焼成後に陶磁器に形成される焼成された絵具層（絵具の無機質成分層）の表面に十分な艶を得ることができる陶磁器の絵付焼成方法を提供することである。
【０００７】
【課題を解決するための手段】
本発明者は、間接加熱型の焼成炉内の酸素濃度は２０体積％程度と高濃度であるが、直接加熱型の焼成炉の酸素濃度は６〜７体積％とかなり希薄になる場合があるため、Ｃｒ2Ｏ3含有無鉛絵具は焼成温度（一般的におよそ８８０℃）付近で発泡が起き、焼成後の絵具の表面に凹凸が生じ十分な艶を得ることができなくなると考えた。
【０００８】
そこで、本発明者は、Ｃｒ2Ｏ3含有無鉛絵具を付着させた陶磁器を直接加熱により絵付焼成する場合には、絵付焼成における焼成帯の少なくとも前半の雰囲気中の酸素の最低濃度を８体積％以上にすることにより、前記無鉛絵具の発泡を防止して、焼成後の絵具の表面に十分な艶を得ることができる、ということを見出し本発明を完成するに至った。
【０００９】
第１の視点において、本発明によれば、Ｃｒ2Ｏ3含有無鉛絵具を付着させた陶磁器を直接加熱型の焼成炉により直接加熱する絵付焼成方法であって、絵付焼成における焼成帯の少なくとも前半の雰囲気中の酸素の最低濃度を８体積％以上にする陶磁器の絵付焼成方法により、上記目的を達成することができる。
【００１０】
絵付焼成は、経過時間と温度の関係により、例えば図１に示すように、焼成可能な温度領域まで温度を上昇させる昇温帯、実質的な焼成を行うことができる温度領域の焼成帯、実質的な焼成を行うことができる温度領域未満に温度を降下させる冷却帯に分けることができる。本発明における「焼成帯」は、このように経過時間と温度の関係により規定される「焼成帯」のことである。
【００１１】
上記本発明の陶磁器の絵付焼成方法は、次のようにすることができる。
【００１２】
絵付焼成の最高温度から１００℃低い温度以上の温度領域であって焼成帯前半までの雰囲気中の酸素の最低濃度を８体積％以上にすることができる。
絵付焼成における８００〜９００℃の温度領域であって焼成帯前半までの雰囲気中の酸素の最低濃度を８体積％以上にすることができる。
絵付焼成における５００〜９００℃の温度領域であって焼成帯前半までの雰囲気中の酸素の最低濃度を８体積％以上にすることができる。
ローラーハースキルンにより直接加熱することができる。
前記雰囲気中の酸素の最低濃度を１０体積％以上にすることができる。
【００１３】
［作用］
Ｃｒ2Ｏ3含有無鉛絵具は、ビヒクル（展色剤）を含有している。Ｃｒ2Ｏ3を含む無鉛絵具の焼成中の発泡量は、焼成温度付近（約５００〜９００℃、特に８００〜９００℃）のビヒクルの残留量に大きく影響を受ける。そこで、焼成温度付近の酸素濃度を高くすることにより、ビヒクルをなるべく低い温度で分解させ発泡を抑制することで、焼成後の絵具の表面に凹凸がなく十分な艶を得ることができる。
【００１４】
なお、焼成温度帯付近での酸素濃度を高めた焼成方法として、特開平５−５８７４６号公報に記載の陶磁器の焼成方法、及び特開平６−９２７６号公報に記載のセラミックの焼成方法があるが、これらは陶磁器類の生地の焼成に関するものであり、絵具の焼成については言及していない。
【００１５】
以下、本発明の好適な実施の形態を説明する。なお、本発明において数値範囲の記載は、両端値のみならず、その中に含まれる全ての任意の中間値を含むものとする。
【００１６】
【発明の実施の形態】
［直接加熱による焼成方法］
Ｃｒ2Ｏ3含有無鉛絵具を付着させた陶磁器は、例えば、直火型バーナーを用いた焼成炉、直接加熱型のローラーハースキルン等により直接加熱することができる。
【００１７】
本発明の陶磁器の絵付焼成方法では、絵付焼成における焼成帯の少なくとも前半の雰囲気中（好ましくは絵付焼成の最高温度から１００℃低い温度以上の温度領域であって焼成帯前半までの雰囲気中、より好ましくは絵付焼成における８００〜９００℃（より好ましくは７００〜９００℃、さらに好ましくは５００〜９００℃）の温度領域であって焼成帯前半までの雰囲気中）の酸素の最低濃度を８体積％以上（好ましくは１０体積％以上、より好ましくは１５体積％以上）にする。８体積％未満であると、ビヒクルの分解が十分に行われずビヒクルないしその灰分が残存し焼成後の艶不良の原因となる。
【００１８】
焼成帯前半までの雰囲気中の酸素の最低濃度の上限は特に限定するものではないが、１５体積％でよく、１３体積％あるいは１２体積％でもよい。絵付焼成における５００〜９００℃の温度領域であって焼成帯前半までの雰囲気中の酸素の濃度範囲は、８〜１５体積％にすることができる。
【００１９】
雰囲気中の酸素の最低濃度を８体積％以上にするためには、雰囲気に空気又は酸素を供給する。直接加熱型による焼成炉の内部の雰囲気中の酸素の最低濃度を８体積％以上にするには、例えば、前記焼成炉の内部の雰囲気中の酸素の最低濃度が８体積％以上になる量で焼成炉の内部に空気又は酸素を供給する。
【００２０】
本発明における陶磁器の絵付焼成方法においては、好ましくは、陶磁器の表面に形成された釉層の表面にＣｒ2Ｏ3含有無鉛絵具を付着させた陶磁器を直接加熱する。
【００２１】
［Ｃｒ2Ｏ3含有無鉛絵具］
Ｃｒ2Ｏ3含有無鉛絵具は、Ｃｒ2Ｏ3と、Ｃｒ2Ｏ3以外の無機質成分と、有機質成分であるビヒクル（展色剤）の混合物である。Ｃｒ2Ｏ3及びこれ以外の無機質成分は、一般的に、粒径５〜１０μｍの粒子状で無鉛絵具に存在している。本発明の絵付焼成方法では次のようなＣｒ2Ｏ3含有無鉛絵具を好適に用いることができる。
【００２２】
Ｃｒ2Ｏ3含有無鉛絵具における、全ての無機質成分とビヒクルの重量比は、１：０．４〜１：１にすることができ、好ましくは１：０．６〜１：０．８である。
【００２３】
Ｃｒ2Ｏ3含有無鉛絵具における、Ｃｒ2Ｏ3とこれ以外の無機質成分の重量比は、１：９９〜４０：６０にすることができ、好ましくは１０：９０〜３０：７０である。
【００２４】
Ｃｒ2Ｏ3含有無鉛絵具におけるＣｒ2Ｏ3の含有率は、１〜４０重量％にすることができ、好ましくは１０〜３０重量％である。
Ｃｒ2Ｏ3含有無鉛絵具におけるＣｒ2Ｏ3以外の無機質成分の含有率は、６０〜９９重量％にすることができ、好ましくは７０〜９０重量％である。
Ｃｒ2Ｏ3含有無鉛絵具におけるビヒクルの含有率は、３０〜５０重量％にすることができ、好ましくは３５〜４５重量％である。
【００２５】
Ｃｒ2Ｏ3以外の無機質成分としては、無鉛絵具に含有させることができる各種の無機質成分、好ましくはフリット等があり、例えば、Ｌｉ2Ｏ、Ｎａ2Ｏ、Ｋ2Ｏ、Ｂ2Ｏ3、Ａｌ2Ｏ3、ＳｉＯ2、ＺｒＯ2、ＭｇＯ、ＣａＯ及びＺｎＯのうちの１種以上を選択して用いることができる。
【００２６】
ビヒクルは、好ましくは、アクリル樹脂及びセルロース樹脂のうちの１種以上の樹脂にすることができ、さらに、溶剤を含有することができる。
【００２７】
【実施例】
以下、本発明の実施例と比較例を示す。
【００２８】
［実施例１］
湿式混合・粉砕した表１の絵具の無機質成分Ａとビヒクル（アクリル樹脂）の重量比が１：０．７５となるように混合してＣｒ2Ｏ3含有無鉛絵具を得て、この無鉛絵具層の厚みが約１６μｍになるように台紙に印刷する。これに厚みが約２０μｍになるようにトップコート（アクリル樹脂）を掛け転写紙（厚み約３６μｍ）を作製する。この転写紙を白磁器に転写し、Ｃｒ2Ｏ3含有無鉛絵具層を付着させた白磁器を得て図１の（ａ）に示す加熱曲線での焼成を行った。
【００２９】
［実施例２］
乾式混合・粉砕した表１の絵具の無機質成分Ｂとビヒクル（アクリル樹脂）の重量比が１：０．７５となるように混合してＣｒ2Ｏ3含有無鉛絵具を得て、この無鉛絵具層の厚みが約１６μｍになるように台紙に印刷する。これに厚みが約２０μｍになるようにトップコート（アクリル樹脂）を掛け転写紙（厚み約３６μｍ）を作製する。この転写紙を白磁器に転写し、Ｃｒ2Ｏ3含有無鉛絵具層を付着させた白磁器を得て図１の（ａ）に示す加熱曲線での焼成を行った。
【００３０】
［比較例１］
湿式混合・粉砕した表１の絵具の無機質成分Ａとビヒクル（アクリル樹脂）の重量比が１：０．７５となるように混合してＣｒ2Ｏ3含有無鉛絵具を得て、この無鉛絵具層の厚みが約１６μｍになるように台紙に印刷する。これに厚みが約２０μｍになるようにトップコート（アクリル樹脂）を掛け転写紙（厚み約３６μｍ）を作成する。この転写紙を白磁器に転写し、Ｃｒ2Ｏ3含有無鉛絵具層を付着させた白磁器を得て図１の（ｂ）に示す加熱曲線での焼成を行った。
【００３１】
［比較例２］
乾式混合・粉砕した表１の絵具の無機質成分Ｂとビヒクル（アクリル樹脂）の重量比が１：０．７５となるように混合してＣｒ2Ｏ3含有無鉛絵具を得て、この無鉛絵具層の厚みが約１６μｍになるように台紙に印刷する。これに厚みが約２０μｍになるようにトップコート（アクリル樹脂）を掛け転写紙（厚み約３６μｍ）を作製する。この転写紙を白磁器に転写し、Ｃｒ2Ｏ3含有無鉛絵具層を付着させた白磁器を得て図１の（ｂ）に示す加熱曲線での焼成を行った。
【００３２】
絵具の無機質成分の詳細な調合を次の表１に示す。また、実施例１〜２及び比較例１〜２で得られた焼成後の絵具層の艶は光沢度で示し、光沢度の測定結果を表２に示す。光沢度の測定はＪＩＳ Ｚ８７４１「鏡面光沢度測定方法」に準じて測定した。測定装置としては、微小平面曲面光度計ＭＭＰ−３００Ａ（日本電飾工業（株）製）を用いた。
【００３３】
【表１】

Figure 0004284403
【００３４】
【表２】
Figure 0004284403
【００３５】
以上のように、本発明によれは、絵具に含まれるフリットの種類、絵具を製造する際の無機質成分（フリットとＣｒ2Ｏ3粒子）の混合・粉砕方法によらずに良好な光沢を有する焼成された絵具層（絵具の無機質成分層）を白磁器に形成することができる。
【００３６】
【発明の効果】
請求項１の陶磁器の絵付焼成方法は、Ｃｒ2Ｏ3含有無鉛絵具を付着させた陶磁器を直接加熱型の焼成炉により直接加熱する絵付焼成方法であって、絵付焼成における焼成帯の少なくとも前半の雰囲気中の酸素の最低濃度を８体積％以上にするので、次の基本的な効果を奏することができる。
【００３７】
生産効率及びエネルギー効率に優れると共に、焼成後、表面に凹凸がなく十分な艶、光沢を有する焼成された絵具層（絵具の無機質成分層）を陶磁器に形成することができる。また、絵具に含まれるフリットの種類、絵具を製造する際の無機質成分（フリットとＣｒ2Ｏ3粒子）の混合・粉砕方法によらずに良好な光沢を有する焼成された絵具層を陶磁器に形成することができる。
【００３８】
請求項２〜６の陶磁器の絵付焼成方法は、それぞれの請求項の構成をさらに具備するので、上記基本的な効果が顕著である。
【００３９】
本発明の陶磁器の絵付焼成方法により絵付した陶磁器は、表面に凹凸がなく十分な艶、光沢を有する焼成された絵具層を有する。
【図面の簡単な説明】
【図１】図１は、経過時間に対する焼成温度及び酸素濃度の関係を示すグラフである。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for firing lead-free paints, and more particularly to a method for firing a ceramic decorated with lead-free paints.
[0002]
[Prior art]
As paints used for decorating ceramics, there are lead paint (lead-containing paint) and lead-free paint. Leaded paints can obtain good color and luster regardless of the firing furnace, but regulations on lead elution from ceramic tableware have been strengthened, and the transition from leaded paints to lead-free paints is being promoted.
[0003]
Prior art relating to lead-free paints is described in Japanese Patent Publication No. 5-53735 which discloses an upper paint for ceramics and a method for producing the same. In the above publication, a frit composed of silicon dioxide, alumina, boron oxide, alkali metal oxide, and containing one or more of rare earth element oxide, hafnium oxide, and group VB group element oxide as a pigment, It describes a lead-free ceramic top paint made by mixing copper carbonate, ferric oxide, antimony trioxide, and cobalt oxide, and the effect is described as being comparable to conventional leaded top paint. .
[0004]
Conventionally, there are lead-free paints containing Cr 2 O 3 as lead-free paints, and ceramics decorated with these lead-free paints that have been painted and fired in an indirect heating type firing furnace such as an electric furnace or a muffle furnace have good gloss Is obtained.
[0005]
[Problems to be solved by the invention]
However, firing in an indirect heating-type firing furnace such as an electric furnace or a muffle furnace has poor production efficiency and energy efficiency. On the other hand, when performing baking with a picture of ceramics decorated with lead-free paints containing Cr 2 O 3 in a direct heating type firing furnace such as roller hearth kiln with better production efficiency and energy efficiency, after firing There was a problem that unevenness occurred on the surface of the paint and sufficient gloss could not be obtained.
[0006]
The object of the present invention is to solve the above-mentioned problems of the prior art, and to obtain a sufficient gloss on the surface of the fired paint layer (inorganic component layer of paint) formed on the ceramic after firing. it is to provide a mETHODS.
[0007]
[Means for Solving the Problems]
The present inventor found that the oxygen concentration in the indirect heating type firing furnace is as high as about 20% by volume, but the oxygen concentration in the direct heating type firing furnace may be considerably dilute at 6-7% by volume. For this reason, it was considered that the lead-free paint containing Cr 2 O 3 was foamed around the firing temperature (generally about 880 ° C.), and the surface of the paint after firing was uneven, making it impossible to obtain sufficient gloss.
[0008]
In view of this, the present inventor, when directly baking a ceramic with a lead-free paint containing Cr 2 O 3 by direct heating, sets the minimum concentration of oxygen in the atmosphere at least in the first half of the baking zone in the baking with 8% by volume. As a result of the above, the present inventors have found that the lead-free paint can be prevented from foaming and that the surface of the paint after firing can be sufficiently glossed, thereby completing the present invention.
[0009]
In a first aspect, according to the present invention, there is provided a baking method with a picture, in which a ceramic to which a lead-free paint containing Cr 2 O 3 is attached is directly heated by a direct heating type baking furnace , and at least the first half of a baking zone in the baking with a picture. The above object can be achieved by a method for firing ceramics with a minimum oxygen concentration of 8% by volume or more.
[0010]
As shown in FIG. 1, for example, as shown in FIG. 1, the baking with a picture is a temperature rising zone that raises the temperature to a temperature range where baking can be performed, a baking zone in a temperature range where substantial baking can be performed, It can be divided into cooling zones in which the temperature is lowered below the temperature range in which proper firing can be performed. The “firing zone” in the present invention is a “firing zone” thus defined by the relationship between elapsed time and temperature.
[0011]
Decorating method for firing ceramics of the upper Symbol present invention can be as follows.
[0012]
The minimum concentration of oxygen in the atmosphere in the temperature range from the highest temperature of painting baking to a temperature lower by 100 ° C. or higher and the first half of the baking zone can be 8% by volume or more.
The minimum concentration of oxygen in the atmosphere up to the first half of the firing zone in the temperature range of 800 to 900 ° C. in the baking with pictures can be 8% by volume or more.
The minimum concentration of oxygen in the atmosphere up to the first half of the firing zone in the temperature range of 500 to 900 ° C. in the baking with pictures can be 8% by volume or more.
It can be heated directly by a roller hearth kiln.
The minimum concentration of oxygen in the atmosphere can be 10% by volume or more.
[0013]
[Action]
The lead-free paint containing Cr 2 O 3 contains a vehicle (color developing agent). The amount of foaming during firing of lead-free paints containing Cr 2 O 3 is greatly affected by the residual amount of vehicle near the firing temperature (about 500 to 900 ° C., particularly 800 to 900 ° C.). Therefore, by increasing the oxygen concentration in the vicinity of the firing temperature, the vehicle is decomposed at a temperature as low as possible to suppress foaming, so that the surface of the paint after firing has no unevenness and a sufficient gloss can be obtained.
[0014]
As a firing method in which the oxygen concentration in the vicinity of the firing temperature zone is increased, there are a ceramic firing method described in JP-A-5-58746 and a ceramic firing method described in JP-A-6-9276. These are related to the firing of ceramic fabrics and do not mention the firing of paints.
[0015]
Hereinafter, preferred embodiments of the present invention will be described. In the present invention, the description of the numerical value range includes not only both end values but also any arbitrary intermediate value included therein.
[0016]
DETAILED DESCRIPTION OF THE INVENTION
[Baking method by direct heating]
The ceramics to which the lead-free paint containing Cr 2 O 3 is attached can be directly heated by, for example, a firing furnace using a direct fire type burner, a direct heating type roller hearth kiln or the like.
[0017]
In the method for firing ceramics according to the present invention, the atmosphere in at least the first half of the firing zone in painting firing (preferably in the atmosphere from the highest temperature of painting firing to a temperature lower than 100 ° C. up to the first half of the firing zone, Preferably, the minimum concentration of oxygen in the temperature range of 800 to 900 ° C. (more preferably 700 to 900 ° C., more preferably 500 to 900 ° C. in the atmosphere up to the first half of the firing zone) in the baking with pictures is 8% by volume or more. (Preferably 10% by volume or more, more preferably 15% by volume or more). If it is less than 8% by volume, the vehicle will not be sufficiently decomposed and the vehicle or its ash will remain, causing poor gloss after firing.
[0018]
The upper limit of the minimum concentration of oxygen in the atmosphere up to the first half of the firing zone is not particularly limited, but may be 15% by volume, 13% by volume, or 12% by volume. The oxygen concentration range in the atmosphere up to the first half of the firing zone in the temperature range of 500 to 900 ° C. in the baking with pictures can be 8 to 15% by volume.
[0019]
In order to make the minimum concentration of oxygen in the atmosphere 8% by volume or more, air or oxygen is supplied to the atmosphere. In order to make the minimum concentration of oxygen in the atmosphere inside the firing furnace by the direct heating type 8% by volume or more, for example, in such an amount that the minimum concentration of oxygen in the atmosphere inside the firing furnace becomes 8% by volume or more. Air or oxygen is supplied to the inside of the firing furnace.
[0020]
In the method for firing ceramics according to the present invention, preferably, the ceramics in which a lead-free paint containing Cr 2 O 3 is adhered to the surface of the glazing layer formed on the surface of the ceramics is directly heated.
[0021]
[Lead-free paint containing Cr 2 O 3 ]
Cr 2 O 3 containing lead-free paint is a Cr 2 O 3, and an inorganic component other than Cr 2 O 3, a mixture of vehicle (Ten'irozai) a organic component. Cr 2 O 3 and other inorganic components are generally present in lead-free paints in the form of particles having a particle size of 5 to 10 μm. In the baking method with a picture of the present invention, the following lead-free paint containing Cr 2 O 3 can be preferably used.
[0022]
In the lead-free paint containing Cr 2 O 3, the weight ratio of all the inorganic components and the vehicle can be 1: 0.4 to 1: 1, preferably 1: 0.6 to 1: 0.8. .
[0023]
In Cr 2 O 3 containing lead-free paint, the weight ratio of the inorganic components other than this and Cr 2 O 3 is 1: 99 to 40: can be 60, preferably 10: 90 to 30: 70.
[0024]
The content of Cr 2 O 3 in the lead-free paint containing Cr 2 O 3 can be 1 to 40% by weight, and preferably 10 to 30% by weight.
Cr 2 O 3 content of inorganic components other than Cr 2 O 3 in the containing lead-free paint may be a 60 to 99% by weight, preferably 70 to 90 wt%.
The content of the vehicle in the lead-free paint containing Cr 2 O 3 can be 30 to 50% by weight, and preferably 35 to 45% by weight.
[0025]
Examples of inorganic components other than Cr 2 O 3 include various inorganic components that can be contained in lead-free paints, preferably frit, such as Li 2 O, Na 2 O, K 2 O, B 2 O 3 , One or more of Al 2 O 3 , SiO 2 , ZrO 2 , MgO, CaO and ZnO can be selected and used.
[0026]
The vehicle may preferably be one or more of an acrylic resin and a cellulose resin, and may further contain a solvent.
[0027]
【Example】
Examples of the present invention and comparative examples are shown below.
[0028]
[Example 1]
A lead-free paint containing Cr 2 O 3 is obtained by mixing so that the weight ratio of the inorganic component A and the vehicle (acrylic resin) in the paint of Table 1 wet-mixed and crushed is 1: 0.75, and this lead-free paint layer Is printed on the mount so that the thickness of the paper becomes about 16 μm. This is coated with a top coat (acrylic resin) so as to have a thickness of about 20 μm to produce a transfer paper (thickness of about 36 μm). This transfer paper was transferred to a white porcelain to obtain a white porcelain to which a lead-free paint layer containing Cr 2 O 3 was adhered, and was fired on the heating curve shown in FIG.
[0029]
[Example 2]
A lead-free paint containing Cr 2 O 3 is obtained by mixing the dry blended and crushed paints of Table 1 so that the weight ratio of the inorganic component B and the vehicle (acrylic resin) is 1: 0.75. Is printed on the mount so that the thickness of the paper becomes about 16 μm. This is coated with a top coat (acrylic resin) so as to have a thickness of about 20 μm to produce a transfer paper (thickness of about 36 μm). This transfer paper was transferred to a white porcelain to obtain a white porcelain to which a lead-free paint layer containing Cr 2 O 3 was adhered, and was fired on the heating curve shown in FIG.
[0030]
[Comparative Example 1]
A lead-free paint containing Cr 2 O 3 is obtained by mixing so that the weight ratio of the inorganic component A and the vehicle (acrylic resin) in the paint of Table 1 wet-mixed and crushed is 1: 0.75, and this lead-free paint layer Is printed on the mount so that the thickness of the paper becomes about 16 μm. This is coated with a top coat (acrylic resin) so that the thickness is about 20 μm, and transfer paper (thickness: about 36 μm) is created. This transfer paper was transferred to a white porcelain to obtain a white porcelain to which a lead-free paint layer containing Cr 2 O 3 was adhered, and was fired on the heating curve shown in FIG.
[0031]
[Comparative Example 2]
A lead-free paint containing Cr 2 O 3 is obtained by mixing the dry blended and crushed paints of Table 1 so that the weight ratio of the inorganic component B and the vehicle (acrylic resin) is 1: 0.75. Is printed on the mount so that the thickness of the paper becomes about 16 μm. This is coated with a top coat (acrylic resin) so as to have a thickness of about 20 μm to produce a transfer paper (thickness of about 36 μm). This transfer paper was transferred to a white porcelain to obtain a white porcelain to which a lead-free paint layer containing Cr 2 O 3 was adhered, and was fired on the heating curve shown in FIG.
[0032]
The detailed formulation of the inorganic components of the paint is shown in Table 1 below. Further, the gloss of the fired paint layers obtained in Examples 1 and 2 and Comparative Examples 1 and 2 is shown in gloss, and the measurement results of gloss are shown in Table 2. The gloss was measured according to JIS Z8741 “Specular Gloss Measurement Method”. As a measuring apparatus, a micro-planar curved surface photometer MMP-300A (manufactured by Nippon Denka Kogyo Co., Ltd.) was used.
[0033]
[Table 1]
Figure 0004284403
[0034]
[Table 2]
Figure 0004284403
[0035]
As described above, according to the present invention, it has a good gloss regardless of the type of frit contained in the paint and the mixing and pulverization method of the inorganic components (frit and Cr 2 O 3 particles) in producing the paint. The fired paint layer (the inorganic component layer of the paint) can be formed on white porcelain.
[0036]
【The invention's effect】
The method for firing a ceramic with a picture according to claim 1 is a method for firing with a picture in which a ceramic to which a lead-free paint containing Cr 2 O 3 is attached is directly heated by a direct heating type firing furnace , at least in the first half of the firing zone in the firing with picture. Since the minimum concentration of oxygen in the atmosphere is 8% by volume or more, the following basic effects can be obtained.
[0037]
A fired paint layer (inorganic component layer of paint) having excellent luster and luster with no unevenness on the surface can be formed on the ceramic after firing, which is excellent in production efficiency and energy efficiency. In addition, the type of frit contained in the paint and the sintered paint layer with good gloss are formed on the ceramics regardless of the mixing and grinding method of the inorganic components (frit and Cr 2 O 3 particles) when the paint is manufactured. can do.
[0038]
Since the method for firing ceramics according to claims 2 to 6 further includes the structure of each claim, the above basic effect is remarkable.
[0039]
Ceramics was decorating by decorating method for firing ceramics of the present invention have a calcined paint layer has a sufficient gloss, gloss no irregularities on the surface.
[Brief description of the drawings]
FIG. 1 is a graph showing a relationship between a firing temperature and an oxygen concentration with respect to an elapsed time.

Claims (6)

Ｃｒ2Ｏ3含有無鉛絵具を付着させた陶磁器を直接加熱型の焼成炉により直接加熱する絵付焼成方法であって、絵付焼成における焼成帯の少なくとも前半の雰囲気中の酸素の最低濃度を８体積％以上にすることを特徴とする陶磁器の絵付焼成方法。A method of painting baking in which a ceramic to which a lead-free paint containing Cr 2 O 3 is adhered is directly heated by a direct heating type firing furnace, wherein the minimum concentration of oxygen in the atmosphere at least in the first half of the firing zone in painting firing is 8% by volume A method for firing ceramics with a picture characterized by the above. 絵付焼成の最高温度から１００℃低い温度以上の温度領域であって焼成帯前半までの雰囲気中の酸素の最低濃度を８体積％以上にすることを特徴とする請求項１に記載の陶磁器の絵付焼成方法。  2. The ceramic picture according to claim 1, wherein the minimum concentration of oxygen in the atmosphere in the atmosphere up to the first half of the firing zone is set to 8% by volume or more in a temperature range of 100 ° C. lower than the highest temperature of the picture firing. Firing method. 絵付焼成における８００〜９００℃の温度領域であって焼成帯前半までの雰囲気中の酸素の最低濃度を８体積％以上にすることを特徴とする請求項１〜２のいずれか一に記載の陶磁器の絵付焼成方法。  The ceramic according to any one of claims 1 to 2, wherein a minimum oxygen concentration in an atmosphere in a temperature range of 800 to 900 ° C in the firing with a picture and up to the first half of the firing zone is 8% by volume or more. The baking method with a picture. 絵付焼成における５００〜９００℃の温度領域であって焼成帯前半までの雰囲気中の酸素の最低濃度を８体積％以上にすることを特徴とする請求項１〜３のいずれか一に記載の陶磁器の絵付焼成方法。  The ceramic according to any one of claims 1 to 3, wherein a minimum oxygen concentration in an atmosphere up to the first half of the firing zone is set to 8% by volume or more in a temperature range of 500 to 900 ° C in painting firing. The baking method with a picture. ローラーハースキルンにより直接加熱することを特徴とする請求項１〜４のいずれか一に記載の陶磁器の絵付焼成方法。  It heats directly with a roller hearth kiln, The baking method with a picture of the ceramics as described in any one of Claims 1-4 characterized by the above-mentioned. 前記雰囲気中の酸素の最低濃度を１０体積％以上にすることを特徴とする請求項１〜５のいずれか一に記載の陶磁器の絵付焼成方法。  The method for firing a ceramic picture according to any one of claims 1 to 5, wherein the minimum concentration of oxygen in the atmosphere is 10% by volume or more.
JP02017699A 1999-01-28 1999-01-28 A method of firing ceramics with lead-free paint containing Cr2O3 Expired - Lifetime JP4284403B2 (en)

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