JP4108504B2

JP4108504B2 - Painting or coloring of heat-resistant materials

Info

Publication number: JP4108504B2
Application number: JP2003045925A
Authority: JP
Inventors: 一▲郎▼ 金氏; 久雄阿部; 雄二高尾
Original assignee: Nagasaki Prefectural Government
Current assignee: Nagasaki Prefectural Government
Priority date: 2003-02-24
Filing date: 2003-02-24
Publication date: 2008-06-25
Anticipated expiration: 2023-02-24
Also published as: JP2004256319A

Description

【０００１】
【発明の属する技術分野】
本発明は、例えば陶磁器、ガラス、ほうろうなどの耐熱性素材の表面に耐熱性の絵付や彩色を施す方法に係り、特に、発色金属元素を含む化合物の水溶液を絵具として用いて耐熱性素材の表面に直接又は間接に絵付け又は彩色ができ、また、この発色金属元素を含む化合物の水溶液を印刷用インクとしてプリンターを用いて、耐熱性素材の表面に直接又は間接に印刷できるようにした耐熱性素材の絵付又は彩色方法に関するものである。
【０００２】
【従来の技術】
従来、例えば陶磁器、ガラス、ほうろうなどの耐熱性素材の表面に耐熱性の絵付や彩色を行うには、以下のような工程を経て行われるのが普通であった。
まず陶磁器の場合について説明すると、陶磁器への絵付はほとんどの場合、素焼段階での下絵付、施釉焼成後のイングレーズ絵付、施釉焼成後の上絵付のいずれかで行われる。下絵付では耐熱性の無機粉体絵具で描画、彩色、印字等を行った後に、施釉し、1200℃以上で本焼成を行って下絵付を完成する。また、イングレーズ絵付では、同じく耐熱性の無機粉体絵具により、施釉、本焼成を終えた陶磁器の表面に、転写又は筆などで描画、彩色し、その後に、通常は1200℃以上の温度で加熱し、絵具粒子を釉中に拡散させ絵付けを定着させる。このように下絵付及びイングレーズ絵付では、いずれも1200℃以上の高温の熱処理を必要とする。一方、上絵付は比較的低融点の上絵具を用いて、施釉、本焼成を終えた陶磁器の表面に絵付、彩色し、通常は750〜850℃程度の温度で熱処理し、上絵を釉表面に溶着させる。
また、金属の表面に彩色する方法としてはほうろうによる方法があるが、金属素材に直接に無機粉体絵具で彩色することはなく、通常は金属との熱膨張歪みを少なくするために、その表面に２層以上のガラス質な無機素材を被覆し、その上に陶磁器と同様に耐熱性の無機粉体絵具を用いて絵付又は彩色を施していた。
さらに、以上は耐熱性素材への直接的な絵付方法に関するが、間接的な絵付方法として主にスクリーン印刷法や銅板印刷法などの印刷技術を用いた方法がある。これらの間接的な方法では、絵付や彩色の絵柄を無機粉体絵具を用いて転写紙などの紙面へ印刷し、その後に陶磁器素焼きや焼成後の釉表面へ転写し、それぞれの焼成を経て絵付が完成する。
以上のように、耐熱性素材の表面に絵付や彩色を施すには、耐熱性の無機粉体絵具を用いる必要がある。無機粉体絵具は、通常、耐熱性の無機顔料にそれぞれが用いられるときの熱処理温度で耐熱性素材の表面に溶着するように媒溶剤を加えて用いられる。耐熱性の無機顔料は、普通は発色金属元素を含む無機材料であり、ジルコンやチタニアなどの耐熱性の結晶に発色金属元素を固溶させたり、発色金属元素を含む無機結晶を耐熱性の物質、例えばジルコンやシリカなどの結晶で被覆して作られる。無機顔料は熱処理によって合成した後、粉砕や分級などの複雑な製造工程を経て作られている。
【０００３】
【発明が解決しようとする課題】
一方、前述した工程を経ない絵付方法として、発色金属元素を含む化合物水溶液を主に素焼き段階で下絵具として用いる方法があるが、この方法は化合物が定着する温度と焼成温度との適合が難しいために、利用できる化合物が限定されたり、また、その後の焼成によって発色金属元素が拡散し、図形や線画などの境界が判然としなくなるといった問題があった。
さらに、このような水溶液絵具をイングレーズ絵付や上絵付に用いようとすると、釉薬には吸水性がないので、化合物水溶液は釉表面ではじかれ、絵付、彩色すること自体が難しいといった問題点があった。
また、既述の印刷技術を用いた間接的な絵付方法では、原版から数段階の製版工程を経て印刷用の版を作製しており、版作製の手間と時間を要することから、大量生産向けの絵付技術となっていて、ごく少量生産向けの絵付技術には適さないといった問題があった。
ところで、ごく少量生産向けの絵付として、前述の耐熱性の無機粉体絵具を印刷用インクとし、インクジェットプリンターを用いて、耐熱性素材の表面に直接又は間接に印刷する方法が考えられるが、無機粉体絵具の無機顔料を遊星ボールミルなどの、かなり強力な微粉砕器によって粉砕し作製した、粒径が0.5μｍ以下の微粒子タイプの印刷用インクであっても、顔料粒子がやがてプリンターのノズルを閉塞させるので、印刷が途中で停止してしまい、現状ではプリンターを用いて耐熱性素材の表面に直接又は間接に印刷することは困難であった。
【０００４】
本発明は、上記のような課題に鑑み、その課題を解決すべく創案されたものであって、その目的とするところは、発色金属元素の化合物と反応して不溶化する定着材を含む下地材を用いることにより、発色金属元素を含む化合物の水溶液絵具が有する上記欠点、つまり焼成後に発色金属元素が拡散し、図形や線画などの境界が判然としなくなる問題や、釉表面ではじかれ、絵付、彩色すること自体が難しいという問題を解消して、発色金属元素を含む化合物の水溶液を絵具として用いて耐熱性素材の表面に直接又は間接に絵付け又は彩色することができると共に、この発色金属元素を含む化合物の水溶液を印刷用インクとしてプリンターを用いて、耐熱性素材の表面に直接又は間接に印刷することのできる耐熱性素材の絵付又は彩色方法を提供することにある。
【０００５】
【課題を解決するための手段】
以上の目的を達成するために、請求項１は、耐熱性素材の表面に耐熱性の絵付又は彩色を施す目的で、発色金属元素の化合物と反応して不溶化する定着材を含む下地材を、耐熱性素材の表面に予め被覆し、その被覆層の上から発色金属元素を含む化合物の水溶液を用いて絵付け又は彩色を施した後、全体を乾燥・熱処理することによって、耐熱性素材の表面に金属元素を定着させる手段よりなるものである。
【０００６】
また、請求項２は、耐熱性素材の表面に耐熱性の絵付又は彩色を施す目的で、発色金属元素の化合物と反応して不溶化する定着材、媒溶材、結合材及び媒液からなる下地材を、耐熱性素材の表面に予め被覆し、その被覆層の上から発色金属元素を含む化合物の水溶液を用いて絵付け又は彩色を施した後、全体を乾燥・熱処理することによって、耐熱性素材の表面に金属元素を定着させる手段よりなるものである。
【０００７】
また、請求項３は、発色金属元素の化合物と反応して不溶化する定着材として消石灰、媒溶材として無色の上絵具、結合材としてメチルセルロース、媒液として水を用いて調製したものからなる下地材を、耐熱性素材としての陶磁器の表面に予め被覆し、発色剤として金属化合物水溶液を用いて陶磁器表面の被覆層の上に絵付又は彩色した後、上絵付焼成することにより、陶磁器表面上に絵付又は彩色を施す手段よりなるものである。
【０００８】
また、請求項４は、デキストリンを被覆した耐熱性素材用の転写紙上に油性のラッカーを塗布しその上に、発色金属元素の化合物と反応して不溶化する定着材を含む下地材を塗布した後に、下地材を塗布した転写紙上に発色金属元素の化合物水溶液で絵付又は彩色を施し、さらにその上から油性ラッカーを塗布して乾燥後、通常の上絵転写と同様に耐熱性素材の表面上に転写し、上絵付焼成することにより、耐熱性素材表面上に絵付又は彩色を施す手段よりなるものである。
【０００９】
また、請求項５は、デキストリンを被覆した耐熱性素材用の転写紙上に油性のラッカーを塗布しその上に、発色金属元素の化合物と反応して不溶化する定着材、媒溶材、結合材及び媒液からなる下地材を塗布した後に、下地材を塗布した転写紙上に発色金属元素の化合物水溶液で絵付又は彩色を施し、さらにその上から油性ラッカーを塗布して乾燥後、通常の上絵転写と同様に耐熱性素材の表面上に転写し、上絵付焼成することにより、耐熱性素材表面上に絵付又は彩色を施す手段よりなるものである。
【００１０】
また、請求項６は、デキストリンを被覆した陶磁器用の転写紙上に油性のラッカーを塗布しその上に、発色金属元素の化合物と反応して不溶化する定着材、媒溶材、結合材及び媒液からなる下地材を塗布した後に、下地材を塗布した転写紙上に発色金属元素の化合物水溶液で絵付又は彩色を施し、さらにその上から油性ラッカーを塗布して乾燥後、通常の上絵転写と同様に耐熱性素材としての施釉陶磁器の表面上に転写し、上絵付焼成することにより、陶磁器表面上に絵付又は彩色を施す手段よりなるものである。
【００１１】
また、請求項７は、デキストリンを被覆した陶磁器用の転写紙上に油性のラッカーを塗布しその上に、発色金属元素の化合物と反応して不溶化する定着材として消石灰、媒溶材として無色の上絵具、結合材としてメチルセルロース、媒液として水を用いて調製したものからなる下地材を塗布した後に、下地材を塗布した転写紙上に発色金属元素の化合物水溶液で絵付又は彩色を施し、さらにその上から油性ラッカーを塗布して乾燥後、通常の上絵転写と同様に耐熱性素材としての施釉陶磁器の表面上に転写し、上絵付焼成することにより、陶磁器表面上に絵付又は彩色を施す手段よりなるものである。
【００１２】
【発明の実施の形態】
以下、本発明をより具体的に説明する。
本発明の耐熱性素材の絵付又は彩色方法は、耐熱性素材の表面に耐熱性の絵付又は彩色を施す目的で、発色金属元素の化合物と反応して不溶化する定着材を含む下地材を、耐熱性素材の表面に予め被覆し、その被覆層の上から発色金属元素を含む化合物の水溶液を用いて絵付又は彩色を施した後、全体を乾燥・熱処理することによって、耐熱性素材の表面に金属元素を定着させることにある。通常、下地材は発色金属元素の化合物と反応して不溶化する定着材、媒溶材、結合材及び媒液等からなる。
【００１３】
耐熱性の素材として陶磁器を用いた場合は、消石灰などの定着材、無色の上絵具などの媒溶材、メチルセルロースなどの結合材、さらに水を媒液として調製した下地材を、施釉陶磁器の表面に被覆して乾燥後に、発色金属元素を含む化合物水溶液を用いて被覆層の上に描画又は彩色した後、上絵付焼成することにより、陶磁器表面上に絵付又は彩色を施す。
【００１４】
上記下地材に用いる定着材としては、上記消石灰の他に炭酸カルシウム、キノリシールなど、金属元素と反応もしくは錯体を形成して難水溶性の化合物となる物質を用いることができる。また、結合材としては上記の他に、ポリビニルアルコールやポリビニルピロリドン系の有機結合材を用いることができる。媒溶材には低融点の市販上絵具を、有鉛、無鉛の如何に依らず用いることができる。媒液は基本的に水を用いるが、乾燥を早めたり、プリンターの印刷方式との適合のためにエチルアルコールなどの有機溶媒を用いることもある。
【００１５】
さらに、下地材の表面に対して用いる水溶性絵具としては、水中での溶解度の大きな金属化合物の水溶液を用いることが基本的に可能で、塩化コバルト、クロム酸アンモニウム、塩化金、硝酸鉄などを必要に応じて中性又は弱酸性で安定化して用いる。
【００１６】
本発明の大きな特長は、絵付又は彩色の方法として、発色金属元素を含む化合物の水溶液をプリンターの印刷用インクとし、インクジェットプリンターを用いて、耐熱性素材の表面に直接又は間接に印刷できることである。
【００１７】
つまり、発色金属元素の化合物と反応して不溶化する定着材を含む下地材を、耐熱性素材の表面に予め被覆し、発色金属元素を含む化合物の水溶液を用いて耐熱性素材表面の被覆層の上に絵付又は彩色した後、上絵付焼成することにより、耐熱性素材表面上に絵付又は彩色を施す方法として、発色金属元素を含む化合物の水溶液をプリンターの印刷用インクとし、スクリーンプロセスやスプレーガン等により下地材を予め被覆した耐熱性素材の表面に直接印刷することにある。また、デキストリンを被覆した耐熱性素材用の転写紙上に油性のラッカーを塗布しその上に、発色金属元素の化合物と反応して不溶化する定着材を含む下地材を塗布した後に、下地材を塗布した転写紙上に発色金属元素の化合物水溶液で絵付又は彩色を施し、さらにその上から油性ラッカーを塗布して乾燥後、通常の上絵転写と同様に耐熱性素材の表面上に転写し、上絵付焼成することにより、耐熱性素材表面上に絵付又は彩色を施す方法として、発色金属元素を含む化合物の水溶液をプリンターの印刷用インクとし、下地材を塗布した転写紙上に印刷して、転写を通じて耐熱性素材の表面に間接印刷することにある。通常、下地材は発色金属元素の化合物と反応して不溶化する定着材、媒溶材、結合材及び媒液等からなる。なお、定着材、媒溶材、結合材及び媒液、並びに発色金属元素を含む化合物の水溶液は、前記の〔００１３〕〜〔００１５〕の説明の通りである。
【００１８】
この点において、本発明の水溶液と異なる無機粉体絵具をプリンターの印刷用インクとして使用する場合には、陶磁器用顔料を遊星ボールミルなどの、かなり強力な微粉砕器によって粉砕し作製した、粒径が0.5μｍ以下の微粒子タイプの印刷用インクであっても、顔料粒子がやがてプリンターのノズルを閉塞させるので、印刷が途中で停止してしまう。
【００１９】
これに対して、本発明のように水溶液をプリンターの印刷用インクとして使用する場合には無機粉体絵具と異なり、プリンターのノズルを閉塞させることがなく、プリンターによる印刷が可能になる。そして、上記プリンターによる印刷が可能になることによる最大の利点は、時間と手間を要した従来の製版工程が不要となることで、ごく少量の生産にも適応でき、印刷工程のコスト低減に効果があるほか、写真デジタルデータなどの画像データをコンピュータから直接印刷することができる等の利点がある。
【００２０】
プリンターによる間接的な絵付は、スライド転写によって行われる。すなわち、デキストリンを被覆した陶磁器用の転写紙の上にまず油性のラッカーを塗布し、その上に前記の下地材を塗布した後に、発色金属元素の化合物水溶液で絵付又は彩色を施し、さらにその上から油性ラッカーを塗布して乾燥後、通常の上絵転写と同様に施釉陶磁器上に転写し、上絵付焼成することにより行われる。
【００２１】
このように下地材を油性のラッカーで挟むのは、下地材とその上から描かれた水溶性の絵具部分が、スライド転写の際に水によって一部溶解し、印刷された描画や彩色が損なわれることを防ぐためである。
【００２２】
次に、上記発明の作用について以下説明する。
本発明による下地材は陶磁器、ほうろう及び油性ラッカーを施した転写紙の表面等に被覆され、その後に発色金属元素の化合物水溶液による絵付が行われると、下地材成分の中の前記定着材がこれと反応して難水溶性の水酸化物等を生成し、絵具成分の拡散、移動を抑制するために、絵付の輪郭や境界の滲みを防止する。
陶磁器やほうろう表面へ直接的に被覆される場合にあっては、そのまま上絵付焼成を行うと、金属水酸化物が金属酸化物になるとともに、下地材中の媒溶剤が溶融して、下地材の層は陶磁器表面やほうろう表面上に絵付・彩色となって定着される。
【００２３】
一方、下地材処理を転写紙上の油性ラッカーの表面に対して行う間接法では、下地材の上にさらに油性ラッカーを被覆した後に、陶磁器やほうろうの表面にスライド転写される。上絵付け焼成による変化は前記の直接的な処理と同様である。
【００２４】
印刷インクとしての発色金属元素の化合物水溶液は、インクを加熱してその圧力で吹き出す方法やピエゾ素子を用いた方法のインクジェット方式のプリンターによる印刷が基本的に可能であり、上記の下地処理材の層の上に印刷することができる。
【００２５】
【実施例１】
市販の無色上絵具粉体92重量部、消石灰8重量部に、水100重量部、メチルセルロース1重量部（予め２重量%の水溶液にしたもの）を加え、遊星ボールミルにて5分間粉砕・混合して作製した下地材懸濁液を、ノズル先端径が100μmの噴霧ガンにとり、施釉陶磁器板の表面に下地材懸濁液を一様に吹き付けた。これを105℃で2h乾燥し下地材被覆陶磁器板とした。次にその表面に20重量%の塩化コバルト水溶液を毛筆に含ませて、太さや濃さを変えながら線引きを行った後、105℃で1h乾燥し、電気炉中800℃で30分間の熱処理を施した。昇温速度は毎時100℃とした。冷後取り出した試料を観察すると、線はいずれも濃青色となっており陶磁器下絵付けの呉須の発色に類似していた。また、強い筆圧で描かれた部分は、弱い筆圧で描かれた部分よりも濃い濃青色となっており、塩化コバルト液量の違いによって濃淡を描き分けることができた。表面光沢は通常の施釉陶磁器のそれと比べて遜色なく、総合的に見て呉須による下絵染め付けとの外見上の違いは認め難かった。
【００２６】
【実施例２】
実施例１と同様に作製した下地材被覆陶磁器板に、いずれも20重量%の、硝酸コバルト、酢酸コバルト、クエン酸コバルト、グルコン酸コバルト及び硫酸コバルト水溶液を用いて、実施例１と同様に毛筆による線引きを行った後、電気炉中800℃で30分間の熱処理を施した。冷後、試料の表面状態を観察すると、発色は酢酸コバルト、硫酸コバルト、クエン酸コバルト、硝酸コバルト、グルコン酸コバルトの順に濃い青色を呈しており、硝酸コバルトの発色が実施例１の塩化コバルトによるものに近く、グルコン酸コバルトによるもの以外は塩化コバルトよりも濃い発色となった。このように、コバルト化合物の種類を変えることでも、濃青色の呈色の濃さを変えることができた。
【００２７】
【実施例３】
実施例１と同様に作製した下地材被覆陶磁器板に、20重量%の塩化コバルト水溶液、1.25重量%のクロム酸アンモニウム水溶液、12.5重量%の塩化金水溶液を用い、実施例１と同様に線引きを行い、電気炉中800℃で30分間の熱処理を施した。冷後、試料の表面を観察すると塩化コバルトによる線は実施例１と同様に濃青色であったが、クロム酸アンモニウムによる線は黄色を、また、塩化金水溶液による線はピンク色を呈していた。さらに、以上の３種の線が交差した箇所は黒色に近い暗褐色を呈していた。このように本発明では、発色の異なる金属元素の化合物水溶液を絵具として用いることで、それぞれの色を同時に発色させることができ、さらに重ねて用いることでその混色も可能なことが分かる。
【００２８】
【実施例４】
市販の無色上絵具粉体92重量部、キノリノール8重量部、もしくは市販の無色上絵具粉体92重量部、キノリノール4重量部、消石灰4重量部に、水100重量部、メチルセルロース1重量部を加え、遊星ボールミルにて５分間粉砕・混合して下地材懸濁液を作製した（以下簡単のため前者をＡ下地材、後者をＢ下地材と記す）。これらの下地材懸濁液を、実施例１と同様に操作して下地材被覆陶磁器板を作製し、その表面に20重量%の塩化コバルト水溶液、1.25重量%のクロム酸アンモニウム水溶液、12.5重量%の塩化金水溶液を用い、実施例１と同様に線引きし、105℃で1h乾燥した後、電気炉中800℃で30分間の熱処理を施した。冷後取り出した試料を観察すると、下地材Ａの試料では、塩化コバルトによる線は暗い濃青色、クロム酸アンモニウム水溶液による線は薄い黄色、塩化金による線は赤紫をそれぞれ呈していた。また下地材Ｂの試料では、塩化コバルトによる線はやや暗い濃青色、クロム酸アンモニウム水溶液による線はやや薄い黄色、塩化金による線は紫がかったピンクをそれぞれ呈していた。キノリノールを用いると全般的に暗色がかった呈色を示したが、線の境界は、実施例１〜４の結果と比べてはっきりしていた。
【００２９】
【実施例５】
ステンレススティールSUS433の板（50×50mm）に市販のほうろう下ぐすり（黒色）を塗布し、電気炉中840℃で３分間加熱して定着させて冷却した後、市販ほうろう上ぐすり（白色）を塗布し、上記と同様に820℃で３分間加熱して試験板を作製した。次にこの試験板の表面に実施例１と同じ下地材を同様に操作して被覆した。さらに実施例３と同様に、20重量%の塩化コバルト水溶液、1.25重量%のクロム酸アンモニウム水溶液、12.5重量%の塩化金水溶液を用いて線引きを行い、電気炉中800℃で30分間の熱処理を施した。冷後取り出した試料を観察すると、塩化コバルトによる線は濃青色、クロム酸アンモニウムによる線は明るい黄色、また塩化金による線はピンク色をそれぞれ呈しており、ほうろう釉の表面においても本発明による絵付、彩色方法は有効であることが分かった。
【００３０】
【実施例６】
陶磁器の上絵付転写用のデキストリン塗布紙（以下転写紙）の表面に油性のラッカー(オーバープリントラッカー、以下OPLと記す）を塗布し送風乾燥後、そのOPL層の上に、実施例１と同様の方法で下地材層を形成させ、下地材被覆転写紙を作製した。次にこの下地材被覆転写紙を市販のインク加熱方式のインクジェットプリンターに通常の印刷用紙と同様に装填した。また、印刷用インク容器内のインクを取り出し、その代わりに実施例３に記載した３種の水溶液と、塩化コバルト30重量部、塩化マンガン25重量部、塩化鉄30重量部及びクロム酸アンモニウム15重量部を混合し20重量%の水溶液（黒色絵具）とを印刷インク容器内に注入した。この印刷インクと前記の下地材被覆転写紙の組み合わせにより、コンピューターの画像処理ソフトを介して、色見本とカラー写真画像の印刷を行った。印刷を行った下地材被覆転写紙の被覆層の上に、さらにOPLを塗布し乾燥した。このOPL層の塗布の目的は、下地材層が水に濡れて水溶性の絵付・彩色が損なわれるのを防ぐことにある。以上のように作製した転写用紙を水中に投入し、デキストリン層を溶解させてOPL層−下地材層−OPL層から台紙を剥離させ、これを施釉陶磁器の表面にスライド転写した。105℃で1h乾燥した後、800℃で30分間熱処理を施し、下地材層を陶磁器釉面に定着させた。冷後取り出した試料を観察すると、色見本では実施例３と同様な呈色が示され、また、写真画像もオリジナルに近い発色と階調により再現された。このように、本発明による絵付、彩色方法は、市販のインク加熱方式のインクジェットプリンターによっても応用可能なことが分かる。
【００３１】
【発明の効果】
以上の記載より明らかなように、本発明に係る耐熱性素材の絵付又は彩色方法によれば、以下のような極めて新規的有益なる効果を奏するものである。
（１）本発明による絵付、彩色方法は、発色金属元素を含む化合物の水溶液絵具が有する上記欠点、つまり焼成後に発色金属元素が拡散し、図形や線画などの境界が判然としなくなる問題や、釉表面ではじかれ、絵付、彩色すること自体が難しいという問題を解消して、発色金属元素を含む化合物の水溶液を絵具として用いて耐熱性素材の表面に直接又は間接に絵付け又は彩色することができ、これにより、施釉陶磁器やほうろうなどの耐熱性素材の表面に対して適用でき、陶磁器製品の呉須による染め付けと同様な発色と表面状態を提供することができる。
（２）本発明による絵付、彩色方法では、用いる金属化合物水溶液の種類を選ぶことにより、多色の絵付、彩色が可能である。
（３）本発明による発色金属元素の化合物水溶液をプリンターの印刷用インクとして使用する場合には無機粉体絵具と異なり、プリンターのノズルを閉塞させることがなく、プリンターによる印刷が可能になる。つまり、本発明による絵付、彩色用の下地材を陶磁器用転写紙に塗布し、発色金属元素の化合物水溶液を印刷用インクとして、この下地材層の上に市販のプリンターを用いてデジタル画像を印刷すると、デジタル画像データの陶磁器製品表面へのスライド転写が可能になる。この転写方法は製版工程を要しない新たな絵付、彩色法である。これにより、時間と手間を要した従来の製版工程が不要となることで、ごく少量の生産にも適応でき、印刷工程のコスト低減に効果があるほか、写真デジタルデータなどの画像データをコンピュータから直接印刷することができる等の利点がある。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for applying heat-resistant painting or coloring to the surface of a heat-resistant material such as ceramics, glass or enamel, and in particular, using an aqueous solution of a compound containing a coloring metal element as a paint. Heat resistance that enables direct or indirect painting or coloring on the surface of a heat-resistant material, using a printer as an ink for printing with an aqueous solution of a compound containing this coloring metal element. It relates to a method of painting or coloring a material.
[0002]
[Prior art]
Conventionally, in order to perform heat-resistant painting and coloring on the surface of a heat-resistant material such as ceramics, glass, and enamel, it has been usually performed through the following steps.
First, the case of ceramics will be described. In most cases, painting on ceramics is performed with either a background painting at the unglazed stage, an inglaze painting after glazing firing, or a top painting after glazing firing. After painting, coloring, printing, etc. with heat-resistant inorganic powder paint, glazing and firing at 1200 ° C. or higher to complete the undercoat. Also, with inglaze painting, using the same heat-resistant inorganic powder paint, draw or color with a transfer or brush on the surface of the ceramic after finishing glazing and firing, and then usually at a temperature of 1200 ° C or higher Heat to spread the paint particles in the bowl and fix the painting. As described above, both the subscript and the inglaze picture require heat treatment at a high temperature of 1200 ° C. or higher. On the other hand, the upper picture is painted and colored on the surface of the ceramic after finishing glazing and main firing, using a relatively low melting point upper paint, and usually heat-treated at a temperature of about 750 to 850 ° C. To weld.
In addition, there is an enamel method as a method of coloring the surface of a metal, but it is not directly colored with an inorganic powder paint on a metal material, and the surface is usually used to reduce the thermal expansion distortion with the metal. Two or more layers of a glassy inorganic material were coated on top of each other and painted or colored using a heat-resistant inorganic powder paint in the same manner as ceramics.
Further, the above description relates to a method for directly painting a heat-resistant material. As an indirect painting method, there is a method mainly using a printing technique such as a screen printing method or a copper plate printing method. In these indirect methods, painting and coloring patterns are printed on paper such as transfer paper using inorganic powder paint, and then transferred to the surface of the ceramic ware or fired firewood. Is completed.
As described above, it is necessary to use a heat-resistant inorganic powder paint for painting or coloring the surface of the heat-resistant material. Inorganic powder paints are usually used by adding a medium solvent so as to be welded to the surface of the heat resistant material at the heat treatment temperature when each is used for the heat resistant inorganic pigment. A heat-resistant inorganic pigment is usually an inorganic material containing a coloring metal element. The coloring metal element is dissolved in a heat-resistant crystal such as zircon or titania, or an inorganic crystal containing a coloring metal element is a heat-resistant substance. For example, coated with crystals such as zircon and silica. Inorganic pigments are synthesized through heat treatment and then subjected to complicated manufacturing processes such as grinding and classification.
[0003]
[Problems to be solved by the invention]
On the other hand, as a painting method that does not go through the above-described steps, there is a method in which an aqueous solution of a compound containing a coloring metal element is mainly used as a lower paint in the unglazed stage, but this method is difficult to match the temperature at which the compound is fixed and the firing temperature. For this reason, there are problems that the compounds that can be used are limited, and that the color forming metal element diffuses by subsequent firing, and the boundaries of figures and line drawings become unclear.
Furthermore, when such an aqueous paint is used for an inglaze or overpaint, the glaze has no water absorption, so the aqueous compound solution is repelled on the surface of the glaze, and it is difficult to paint and color itself. there were.
In addition, the indirect painting method using the printing technique described above produces printing plates from the original plate through several plate making processes, which requires time and effort for plate production. However, there was a problem that it was not suitable for painting technology for very small-scale production.
By the way, a method for printing directly or indirectly on the surface of a heat-resistant material using an ink jet printer as a printing ink with the above-mentioned heat-resistant inorganic powder paint as a picture for very small-scale production is considered. Even if it is a fine particle type printing ink with a particle size of 0.5 μm or less, which is made by grinding inorganic pigments in powder paint with a fairly powerful pulverizer such as a planetary ball mill, the pigment particles will eventually open the nozzles of the printer. Since it is blocked, printing stops halfway, and it is difficult to print directly or indirectly on the surface of the heat-resistant material using a printer at present.
[0004]
The present invention has been devised in view of the problems as described above, and has been devised to solve the problems. The object of the present invention is to provide a base material including a fixing material that reacts with a compound of a coloring metal element to insolubilize it. By using the above-mentioned drawbacks of the aqueous paint of a compound containing a color forming metal element, that is, the problem that the color forming metal element diffuses after firing and the boundary of figures and line drawings becomes unclear, The coloring metal element can be directly or indirectly painted or colored on the surface of the heat-resistant material by using an aqueous solution of a compound containing a coloring metal element as a paint, eliminating the problem that coloring itself is difficult. A method of painting or coloring a heat-resistant material that can be printed directly or indirectly on the surface of the heat-resistant material using a printer with an aqueous solution of the compound containing It is to.
[0005]
[Means for Solving the Problems]
In order to achieve the above object, claim 1 is provided with a base material including a fixing material that reacts with a compound of a coloring metal element and insolubilizes for the purpose of applying heat-resistant painting or coloring to the surface of the heat-resistant material. The surface of the heat-resistant material is coated on the surface of the heat-resistant material in advance, painted or colored with an aqueous solution of a compound containing a coloring metal element on the coating layer, and then dried and heat-treated as a whole. It comprises a means for fixing the metal element.
[0006]
Further, the second aspect of the present invention provides a base material comprising a fixing material, a solvent material, a binding material, and a liquid medium which reacts with a compound of a coloring metal element to insolubilize the surface of the heat-resistant material for the purpose of giving a heat-resistant picture or coloring. Is coated on the surface of the heat-resistant material in advance, painted or colored using an aqueous solution of a compound containing a coloring metal element on the coating layer, and then dried and heat-treated as a whole, And a means for fixing a metal element on the surface of the substrate.
[0007]
Further, the present invention provides a base material comprising a slaked lime as a fixing material that reacts with a compound of a coloring metal element to insolubilize, a colorless upper paint as a solvent, methylcellulose as a binder, and water as a medium. Is coated on the surface of the ceramic as a heat-resistant material, painted or colored on the surface of the ceramic surface using a metal compound aqueous solution as a color former, and then painted on the surface of the ceramic. Alternatively, it comprises means for coloring.
[0008]
According to a fourth aspect of the present invention, an oil-based lacquer is applied on a transfer paper for heat-resistant material coated with dextrin, and a base material including a fixing material that reacts with a compound of a coloring metal element and insolubilizes is applied thereon. Then, paint or color with a coloring metal element compound aqueous solution on the transfer paper coated with the base material, and then apply oil-based lacquer on it and dry it on the surface of the heat-resistant material in the same way as with normal picture transfer It is composed of means for painting or coloring the surface of the heat-resistant material by transferring and baking with an overpaint.
[0009]
Further, the present invention relates to a fixing material, a solvent, a binder, and a medium which are coated with an oil-based lacquer on a transfer paper for heat-resistant material coated with dextrin and then insolubilized by reacting with a compound of a coloring metal element. After applying a base material made of a liquid , apply a painting or coloring with a compound metal element aqueous solution on the transfer paper coated with the base material, and then apply an oily lacquer from the top and dry it, Similarly, it comprises means for painting or coloring the surface of the heat-resistant material by transferring it onto the surface of the heat-resistant material and baking it with an overpaint.
[0010]
Further, according to the present invention, an oil-based lacquer is coated on a transfer paper for ceramics coated with dextrin, and a fixing material, a solvent, a binder, and a liquid that react with a compound of a coloring metal element to be insolubilized thereon. After applying the base material, apply a painting or coloring with a coloring metal element compound aqueous solution on the transfer paper coated with the base material, and then apply oily lacquer from the top and dry it, in the same way as normal top picture transfer It consists of means for painting or coloring the surface of the ceramic by transferring it onto the surface of a glazed ceramic as a heat-resistant material and baking it with an overpaint.
[0011]
Further, according to the present invention, slaked lime is used as a fixing material which is insolubilized by applying an oily lacquer on a transfer paper for ceramics coated with dextrin, and then is insolubilized by reacting with a compound of a coloring metal element. Then, after applying a base material made of methyl cellulose as a binder and water as a liquid medium, the transfer paper coated with the base material is painted or colored with an aqueous compound solution of a coloring metal element, and from above After applying oil-based lacquer and drying, it is transferred to the surface of glazed ceramics as a heat-resistant material in the same way as ordinary over-the-picture transfer, and then fired with over-painting, thereby painting or coloring on the ceramic surface. Is.
[0012]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described more specifically.
The method of painting or coloring a heat-resistant material of the present invention is a method for applying a heat-resistant painting or coloring to a surface of a heat-resistant material with a base material containing a fixing material that reacts with a compound of a coloring metal element and insolubilizes. The surface of the heat-resistant material is coated on the surface of the heat-resistant material in advance and painted or colored with an aqueous solution of a compound containing a coloring metal element on the coating layer. It is to fix elements. Usually, the base material is composed of a fixing material, a solvent material, a binding material, a liquid medium, and the like that are insolubilized by reacting with the compound of the coloring metal element.
[0013]
When using ceramics as a heat-resistant material, a fixing material such as slaked lime, a solvent material such as colorless upper paint, a binding material such as methylcellulose, and a base material prepared using water as a medium are applied to the surface of the glazed ceramics. After coating and drying, drawing or coloring on the coating layer using a compound aqueous solution containing a coloring metal element, and then painting or coloring on the surface of the ceramic by baking with an overpaint.
[0014]
As the fixing material used for the base material, in addition to the slaked lime, a substance that forms a poorly water-soluble compound by reacting or forming a complex with a metal element, such as calcium carbonate or quinori seal, can be used. In addition to the above, polyvinyl alcohol or polyvinyl pyrrolidone organic binder can be used as the binder. A commercially available paint having a low melting point can be used as the solvent material regardless of whether it is leaded or lead-free. Water is basically used as the liquid medium, but an organic solvent such as ethyl alcohol may be used for quick drying or compatibility with the printing method of the printer.
[0015]
Furthermore, as a water-soluble paint used for the surface of the base material, it is basically possible to use an aqueous solution of a metal compound having high solubility in water, such as cobalt chloride, ammonium chromate, gold chloride, iron nitrate, etc. Use as neutral or weakly acidic as necessary.
[0016]
A major feature of the present invention is that, as a method of painting or coloring, an aqueous solution of a compound containing a coloring metal element can be used as a printing ink for a printer and can be directly or indirectly printed on the surface of a heat-resistant material using an ink jet printer. .
[0017]
In other words, the surface of the heat-resistant material is coated with a base material containing a fixing material that reacts with the coloring metal element compound to insolubilize in advance, and an aqueous solution of the compound containing the coloring metal element is used to form a coating layer on the surface of the heat-resistant material. As a method of painting or coloring the surface of a heat-resistant material by painting or coloring it on the surface and then baking or painting it on the surface of the heat-resistant material, an aqueous solution of a compound containing a coloring metal element is used as a printing ink for a printer. It is to directly print on the surface of a heat-resistant material that has been coated with a base material in advance. Also, apply an oil-based lacquer on transfer paper for heat-resistant materials coated with dextrin, and then apply a base material containing a fixing material that reacts with the coloring metal element compound to insolubilize it, and then apply the base material. Painted or painted with a coloring metal element compound aqueous solution on the transfer paper, further coated with oil-based lacquer and dried, then transferred onto the surface of the heat-resistant material in the same way as normal top transfer, with top picture As a method of painting or coloring on the heat-resistant material surface by baking, an aqueous solution of a compound containing a coloring metal element is used as printing ink for a printer, printed on a transfer paper coated with a base material, and heat-resistant through transfer. Indirect printing on the surface of the material. Usually, the base material is composed of a fixing material, a solvent material, a binding material, a liquid medium, and the like that are insolubilized by reacting with the compound of the coloring metal element. The fixing solution, the medium, the binder and the medium, and the aqueous solution of the compound containing the coloring metal element are as described in the above [0013] to [0015].
[0018]
In this regard, when using an inorganic powder paint different from the aqueous solution of the present invention as a printing ink for a printer, the particle size produced by pulverizing the ceramic pigment with a fairly powerful pulverizer such as a planetary ball mill. Even if it is a fine particle type printing ink having a particle size of 0.5 μm or less, since the pigment particles eventually block the nozzle of the printer, printing stops halfway.
[0019]
In contrast, when an aqueous solution is used as printing ink for a printer as in the present invention, unlike an inorganic powder paint, printing by a printer is possible without blocking the nozzle of the printer. The biggest advantage of printing with the printer is that it eliminates the need for time-consuming and time-consuming conventional plate-making process, which can be applied to a very small amount of production and is effective in reducing the cost of the printing process. In addition, there is an advantage that image data such as photographic digital data can be printed directly from a computer.
[0020]
Indirect painting with a printer is performed by slide transfer. That is, an oily lacquer is first applied on a transfer paper for ceramics coated with dextrin, and the base material is applied thereon, followed by painting or coloring with a colored metal element compound aqueous solution, and further After applying an oil-based lacquer and drying, it is transferred onto a glazed porcelain in the same manner as a normal overprint transfer, and baked with an overcoat.
[0021]
The base material is sandwiched between oily lacquers in this way because the base material and the water-soluble paint part drawn from above are partially dissolved by water during slide transfer, and the printed drawing and coloring are impaired. This is to prevent this.
[0022]
Next, the operation of the above invention will be described below.
The base material according to the present invention is coated on the surface of transfer paper coated with ceramics, enamel and oil-based lacquer, and then painted with an aqueous solution of a coloring metal element compound, the fixing material in the base material component In order to produce a hardly water-soluble hydroxide and the like, and to prevent the diffusion and movement of the paint components, bleeding of outlines and boundaries of the picture is prevented.
If the ceramic or enamel surface is directly coated, if baking is performed as it is, the metal hydroxide becomes a metal oxide and the solvent in the base material melts. This layer is fixed on the ceramic or enamel surface with a picture or color.
[0023]
On the other hand, in the indirect method in which the base material treatment is performed on the surface of the oil-based lacquer on the transfer paper, the base material is further coated with the oil-based lacquer, and then transferred onto the surface of the ceramic or enamel. The change due to the overpainting firing is the same as the direct processing described above.
[0024]
A coloring metal element compound aqueous solution as a printing ink can basically be printed by an ink jet printer using a method in which the ink is heated and blown at the pressure, or a method using a piezo element. Can be printed on the layer.
[0025]
[Example 1]
100 parts by weight of water and 1 part by weight of methylcellulose (previously 2% by weight aqueous solution) are added to 92 parts by weight of commercially available colorless upper paint powder and 8 parts by weight of slaked lime, and then ground and mixed for 5 minutes in a planetary ball mill. The base material suspension prepared in this manner was taken by a spray gun having a nozzle tip diameter of 100 μm, and the base material suspension was sprayed uniformly on the surface of the glazed ceramic plate. This was dried at 105 ° C. for 2 hours to obtain a base material-coated ceramic plate. Next, a 20% by weight cobalt chloride aqueous solution was added to the surface of the brush, and after drawing while changing the thickness and thickness, it was dried at 105 ° C for 1 h, and heat-treated at 800 ° C for 30 minutes in an electric furnace. gave. The heating rate was 100 ° C./hour. When the samples taken out after cooling were observed, all the lines were dark blue, similar to the color of Kuresu painted in ceramics. In addition, the portion drawn with a strong writing pressure was darker blue than the portion drawn with a weak writing pressure, and the shades could be drawn according to the difference in the amount of cobalt chloride solution. The surface gloss was inferior to that of ordinary glazed ceramics, and it was difficult to recognize the difference in appearance from the original dyeing by Wusu.
[0026]
[Example 2]
A brush similar to that in Example 1 using 20% by weight of cobalt nitrate, cobalt acetate, cobalt citrate, cobalt gluconate and cobalt sulfate aqueous solution on the base material-coated ceramic plate produced in the same manner as in Example 1. After wire drawing, heat treatment was performed in an electric furnace at 800 ° C. for 30 minutes. When the surface state of the sample was observed after cooling, the color development was dark blue in the order of cobalt acetate, cobalt sulfate, cobalt citrate, cobalt nitrate, and cobalt gluconate, and the color development of cobalt nitrate was due to the cobalt chloride of Example 1. The color was darker than that of cobalt chloride except for the product of cobalt gluconate. Thus, the intensity of the dark blue color could be changed by changing the type of the cobalt compound.
[0027]
[Example 3]
Using a 20% by weight cobalt chloride aqueous solution, a 1.25% by weight ammonium chromate aqueous solution and a 12.5% by weight gold chloride aqueous solution on the base material-coated ceramic plate produced in the same manner as in Example 1, drawing was performed in the same manner as in Example 1. Heat treatment was performed in an electric furnace at 800 ° C. for 30 minutes. When the surface of the sample was observed after cooling, the cobalt chloride line was dark blue as in Example 1, but the ammonium chromate line was yellow and the gold chloride aqueous solution line was pink. . Furthermore, the location where the above three lines intersected exhibited a dark brown color close to black. In this way, in the present invention, it can be seen that by using metallic element compound aqueous solutions with different colors as paints, the respective colors can be developed simultaneously, and further, the colors can be mixed by overlapping.
[0028]
[Example 4]
Add 100 parts of water and 1 part by weight of methylcellulose to 92 parts by weight of commercially available colorless upper paint powder, 8 parts by weight of quinolinol, or 92 parts by weight of commercially available colorless upper paint powder, 4 parts by weight of quinolinol, and 4 parts by weight of slaked lime. Then, a base material suspension was prepared by pulverizing and mixing for 5 minutes in a planetary ball mill (for the sake of simplicity, the former is referred to as A base material and the latter as B base material). These base material suspensions were operated in the same manner as in Example 1 to prepare a base material-coated ceramic plate. On the surface, 20% by weight cobalt chloride aqueous solution, 1.25% by weight ammonium chromate aqueous solution, 12.5% by weight Was drawn in the same manner as in Example 1, dried at 105 ° C. for 1 h, and then heat-treated at 800 ° C. for 30 minutes in an electric furnace. When the sample taken out after cooling was observed, in the sample of the base material A, the line due to cobalt chloride was dark dark blue, the line due to the aqueous ammonium chromate solution was light yellow, and the line due to gold chloride was reddish purple. In the sample of the base material B, the cobalt chloride line exhibited a slightly dark blue color, the ammonium chromate aqueous solution line exhibited a slightly light yellow color, and the gold chloride line exhibited a purplish pink color. When quinolinol was used, the coloration was generally dark, but the line boundaries were clear compared to the results of Examples 1-4.
[0029]
[Example 5]
Apply a commercially available enamel paste (black) to a stainless steel SUS433 plate (50 x 50 mm), heat and fix at 840 ° C for 3 minutes in an electric furnace, cool, and then commercially available enamel paste (white) And a test plate was prepared by heating at 820 ° C. for 3 minutes in the same manner as described above. Next, the same base material as that of Example 1 was coated on the surface of the test plate in the same manner. Further, in the same manner as in Example 3, drawing was performed using 20% by weight cobalt chloride aqueous solution, 1.25% by weight ammonium chromate aqueous solution, and 12.5% by weight gold chloride aqueous solution, followed by heat treatment at 800 ° C. for 30 minutes in an electric furnace. gave. When the sample taken out after cooling was observed, the cobalt chloride line was dark blue, the ammonium chromate line was bright yellow, and the gold chloride line was pink. The coloring method was found to be effective.
[0030]
[Example 6]
Apply the oil-based lacquer (overprint lacquer, hereinafter referred to as OPL) to the surface of the dextrin coated paper (hereinafter referred to as transfer paper) for the ceramic top-painted transfer, blow dry, and then on the OPL layer as in Example 1. A base material layer was formed by the above method to prepare a base material-coated transfer paper. Next, the base material-coated transfer paper was loaded into a commercially available ink heating type ink jet printer in the same manner as normal printing paper. Also, the ink in the printing ink container is taken out, and instead of the three aqueous solutions described in Example 3, cobalt chloride 30 parts by weight, manganese chloride 25 parts by weight, iron chloride 30 parts by weight and ammonium chromate 15 parts by weight. The parts were mixed and a 20% by weight aqueous solution (black paint) was poured into the printing ink container. By combining this printing ink and the above base material-coated transfer paper, a color sample and a color photographic image were printed through image processing software of a computer. On the coating layer of the base material-coated transfer paper on which printing was performed, OPL was further applied and dried. The purpose of applying the OPL layer is to prevent the base material layer from getting wet with water and damaging water-soluble painting and coloring. The transfer paper prepared as described above was put into water, the dextrin layer was dissolved, the backing paper was peeled off from the OPL layer-underlying material layer-OPL layer, and this was slid onto the surface of the glazed ceramic. After drying at 105 ° C. for 1 hour, heat treatment was performed at 800 ° C. for 30 minutes to fix the base material layer on the ceramic surface. When the sample taken out after cooling was observed, the color sample showed a coloration similar to that in Example 3, and the photographic image was also reproduced with color development and gradation close to the original. Thus, it can be seen that the painting and coloring method according to the present invention can also be applied to a commercially available ink heating type ink jet printer.
[0031]
【The invention's effect】
As is clear from the above description, according to the method of painting or coloring a heat-resistant material according to the present invention, the following extremely beneficial effects can be obtained.
(1) The painting and coloring method according to the present invention has the above-mentioned drawbacks of the aqueous solution paint of the compound containing a coloring metal element, that is, the problem that the coloring metal element diffuses after firing and the boundary of figures and line drawings becomes unclear. Resolve the problem that it is difficult to repel, paint, and color itself on the surface, and paint or color the surface of the heat-resistant material directly or indirectly using an aqueous solution of a compound containing a coloring metal element as a paint. Thus, it can be applied to the surface of heat-resistant materials such as glazed ceramics and enamels, and can provide the same color and surface condition as the dyeing of ceramic products by Wusu.
(2) In the painting and coloring method according to the present invention, multicolor painting and coloring are possible by selecting the type of the metal compound aqueous solution to be used.
(3) When the aqueous solution of a compound of a color forming metal element according to the present invention is used as a printing ink for a printer, unlike an inorganic powder paint, printing by the printer is possible without blocking the nozzle of the printer. In other words, a base material for painting and coloring according to the present invention is applied to a transfer paper for ceramics, and a digital image is printed on the base material layer by using a commercially available printer on the base material layer as a printing ink using a compound metal element aqueous solution. Then, slide transfer of digital image data to the surface of the ceramic product becomes possible. This transfer method is a new painting and coloring method that does not require a plate making process. This eliminates the need for time-consuming and time-consuming conventional plate-making processes, making it possible to adapt to very small productions and reducing the cost of the printing process. In addition, image data such as photographic digital data can be transferred from a computer. There are advantages such as direct printing.

Claims

For the purpose of applying heat-resistant painting or coloring to the surface of the heat-resistant material, the surface of the heat-resistant material is coated in advance with a base material including a fixing material that reacts with the compound of the coloring metal element and insolubilizes. A heat-resistant material characterized in that the metal element is fixed on the surface of the heat-resistant material by painting or coloring with an aqueous solution of a compound containing a coloring metal element from above and then drying and heat-treating the whole. Painting or coloring method.

For the purpose of applying heat-resistant painting or coloring to the surface of the heat-resistant material, the base material composed of a fixing material, a solvent, a binder and a liquid medium that reacts with the color-forming metal element compound to insolubilize the surface of the heat-resistant material. Pre-coated, painted or colored from above the coating layer with an aqueous solution of a compound containing a coloring metal element, and then dried and heat treated to fix the metal element to the surface of the heat-resistant material. A method of painting or coloring a heat-resistant material, characterized in that

As a heat-resistant material, a base material made of slaked lime as a fixing material that insolubilizes by reacting with a compound of a coloring metal element, a colorless upper paint as a solvent, methylcellulose as a binder, and water as a medium The ceramic surface is pre-coated, and a metal compound aqueous solution is used as a color former. After painting or coloring on the ceramic surface coating layer, the ceramic surface is painted or colored by baking with the top painting. A method for painting or coloring heat-resistant materials.

Applying an oil-based lacquer on a transfer paper for heat-resistant materials coated with dextrin, and then applying a base material containing a fixing material that reacts with the coloring metal element compound to insolubilize, and then apply the base material. Paint or color with a colored metal element compound aqueous solution on paper, apply oil-based lacquer from it, dry it, transfer it onto the surface of heat-resistant material in the same way as normal top transfer, and bake with top A method of painting or coloring a heat-resistant material, characterized in that the surface of the heat-resistant material is painted or colored.

Thereon oily lacquer was coated on the transfer sheet for heat-resistant material coated with dextrin, fixing material to insolubilize by reacting with compounds of the coloring metal elements, medium welding material, a base material made of a binder and medium liquid coating After that, paint or color with a coloring metal element compound aqueous solution on the transfer paper coated with the base material, and then apply oil-based lacquer on it and dry it. A method of painting or coloring a heat-resistant material, wherein the image is painted or colored on the surface of the heat-resistant material by transferring it onto the surface and baking it with a painting.

After applying an oil-based lacquer on a dextrin-coated ceramic transfer paper, and then applying a base material composed of a fixing material, a solvent, a binder, and a medium that reacts with the coloring metal element compound to insolubilize it. Glazed porcelain as a heat-resistant material in the same way as ordinary over-the-picture transfer, after painting or coloring with a coloring metal element compound aqueous solution on the transfer paper coated with the base material, and then applying oil-based lacquer from the top and drying. A method of painting or coloring a heat-resistant material, wherein the painting or coloring is performed on the surface of the ceramic by transferring it onto the surface of the ceramic and baking it with a painting.

An oily lacquer is applied to a transfer paper for ceramics coated with dextrin, on which slaked lime is used as a fixing material that reacts with a compound of a colored metal element to insolubilize, colorless upper paint as a solvent, methylcellulose as a binder, medium After applying a base material made of water as a liquid, apply a painting or coloring with a coloring metal element compound aqueous solution on the transfer paper to which the base material has been applied, and then apply an oily lacquer from there to dry After that, it is transferred onto the surface of glazed ceramic as a heat-resistant material in the same way as the usual transfer of the upper picture, and is painted or colored on the surface of the ceramic by baking with the upper picture. Or coloring method.