JP2004345882A - Paint for pottery - Google Patents
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- JP2004345882A JP2004345882A JP2003142903A JP2003142903A JP2004345882A JP 2004345882 A JP2004345882 A JP 2004345882A JP 2003142903 A JP2003142903 A JP 2003142903A JP 2003142903 A JP2003142903 A JP 2003142903A JP 2004345882 A JP2004345882 A JP 2004345882A
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Abstract
Description
【０００１】
【発明の属する技術分野】
本発明は、新規な陶磁器用絵具および陶磁器絵具の使用方法に関し、取扱いが簡便であり、新しい彩色表現を実施可能とした陶磁器用絵具、およびそれを用いた陶磁器絵具の使用方法に関する。
【０００２】
【従来技術および発明が解決しようとする課題】
従来、和洋食器，装飾品等の製造工程は、基本的には、原材料処理工程、成形工程、乾燥、焼成工程からなる。一般に、未焼成の成形品は素焼される。素焼後、施釉され、さらに本焼される。絵付けを陶磁器表面に施す場合、従来、施釉後乾燥した生地に下絵付けを行い、透明釉薬をかけてから本焼きを行う。その上に上絵付けを行う場合は、絵付けを行ってからさらに焼成し製品とする。乾燥させた釉薬の表面に絵付けを行う場合、釉薬の表面は釉薬の粉を一面にふいた状態であり、絵付けの筆に粉状の釉薬がからんで筆の円滑な運びを阻害し、細筆を用いて行う繊細な表現をすることができなかった。また、絵付けの際の絵具の水分で釉薬が緩み、絵具と混ざったり、釉薬の表面性が損なわれる問題があった。
【０００３】
また、乾燥釉薬上に絵付けする場合、釉薬表面の粉末が絵付け工程に影響させないために、釉薬の表面を固定化させる改良が加えられていた。具体的には、釉薬中に樹脂等のバインダーを付加し樹脂膜を表面に形成させる方法が提案された（例えば、特許文献１）。特許文献１は、合成樹脂エマルジョンまたは水溶性高分子、またはそれらの混合物を主体とするプライマーを生釉層表面に施した後、ついで転写用絵柄を密着させ、釉薬の熟成と絵柄層の焼成とを同時に行う方法が開示されている。
【０００４】
しかしながら、上記の方法で熱処理工程は１回と簡略化されたが、生釉上に水を多く含む高分子水溶液、つまりプライマーを塗布するために、釉薬層を傷つけるおそれがあった。
【０００５】
また、釉薬に、絵柄層と密着性が良好で耐水性に富む樹脂水性エマルジョンを配合し、さらに界面活性剤を含む組成物を用いて、施釉とプライマー処理を１つの工程とする方法が提案されている（例えば、特許文献２）。
【０００６】
しかし、釉薬に含まれる樹脂が、加熱分解されて有害なガスが発生したり、焼成の際に炭化してその痕跡が絵付けに影響するおそれがあった。
【０００７】
あるいは、素焼生地に施釉し乾燥後焼成して、その後絵付けを行うチャイナペイントを用いて絵付けを行い、さらに焼成する方法がある。従来用いられていた絵具は、顔料を透して下地の色が最終的な発色に影響していた。透明釉薬の場合は、陶磁器の生地の色、釉薬に着色している場合は、その着色釉薬の色に、絵付けの絵具の色が左右される。このため、これを計算して彩色を施さねばならず、下地の色と混色した結果、発現した色は、鮮やかさに欠ける。従って、彩色を映えさせるためには、陶磁器の材料は、より白色に近い乳白色を有すること、さらに釉薬の色は、白色に近い色が要求されてきた。
【０００８】
チャイナペイントを用いた絵付け方法では、通常、パレット上で顔料と油性メジウムを混練しつつ絵付けを行うが、顔料とメジウムの配合割合が使用の都度変化せざるを得ない。また、使用した筆はその都度テレピン油で洗浄しなければならず、油性の溶剤の臭いが作業場の周辺に充満したり、また筆の傷みが激しい等の問題があった。さらに、絵具は固化しやすく扱いが繁雑であり、また、チューブ入りの絵具は、チューブの中で成分の分離が発生し、経時変化に伴ない顔料がチューブ中で固化してしまう等の問題があった。
【０００９】
さらに、素焼の素地に絵付けを施し、透明釉薬をかけて焼成する絵付け方法もある。この場合、素焼の素地そのものの有する吸水性により、絵具の水分が吸収されるため、筆の運びやが制限され、熟練しなければ伸びやかなタッチや繊細な細線を描くことは望めない。
【００１０】
【発明が解決しようとする課題】
本発明者らは、上述したような従来行なわれてきた陶磁器の製法における種々の問題を解決し、簡便に扱え、陶磁器の製造工程を簡略化できコストダウンが図れ、さらに繊細な表現を可能とした新たな陶磁器用絵具の開発を目指し、鋭意研究の結果本発明を完成した。
【００１１】
【特許文献１】
特開昭５４−８１３１６号公報
【特許文献２】
特公平７−４５３５１号公報
【００１２】
【課題を解決するための手段】
本発明の陶磁器用絵具は、少なくとも、着色基材、水溶性バインダーを含み、水溶性バインダーが、ポリアルキレンオキシド系水溶性樹脂である。
【００１３】
本発明の陶磁器用絵具は、着色基材１００重量部に対し、ポリアルキレンオキシド系水溶性樹脂２０〜８０重量部を含み得る。特には、着色基材１００重量部に対し、ポリアルキレンオキシド系水溶性樹脂３０〜６０重量部含み得る。
【００１４】
ここで、前記着色基材は、無機顔料を含み、無機顔料は、シリカ、アルミナ、またはシリカとアルミナの複合体からなる群から選択される１つと、金属酸化物の組合せを固溶したものである。
【００１５】
上記無機顔料は、粒径１μｍ〜１０μｍであり得る。
【００１６】
ここで、上記ポリアルキレンオキシド系水溶性樹脂が、ヒドロキシ基含有化合物と、多官能イソシアネートまたは多官能カルボン酸またはその誘導体とを反応させて得られる、重量平均分子量１万以上の親水性高分子量化合物であり得る。
【００１７】
本発明の陶磁器用絵具の他の態様としては、顔料、ポリアルキレンオキシド系水溶性樹脂、乾燥調整剤を含み、固形状であり得る。
【００１８】
ここで、乾燥調整剤が、ポリエチレングリコールであり得る。
【００１９】
また、上記着色基材は、無機顔料、および釉薬を含みうる。
【００２０】
本発明の陶磁器は、上記いずれかに記載の陶磁器用絵具を用いて彩色され得る。
【００２１】
また、本発明の陶磁器の製造方法は、素焼成形品を準備する工程、
素焼成形品表面に、上記いずれかに記載の陶磁器用絵具を用いて絵付けを行う工程、
焼成する工程とで構成されうる。
【００２２】
【発明の実施の形態】
本発明にかかる陶磁器用絵具は、顔料、バインダーを含み、ここで、バインダーは、ポリアルキレンオキシド系水溶性樹脂である。本発明の陶磁器用絵具は、水により随意に顔料の濃度を変化させることができ、乾燥した釉薬の表面であっても、焼成した釉薬の表面、あるいは素焼した成形品の表面であっても、それぞれの下地の色に左右されず、鮮やかな一定の色調を発現することができる。
【００２３】
本発明に用いられる着色基材は、無機顔料を含み得る。無機顔料は、シリカ、アルミナ、あるいはシリカとアルミナの複合体に、酸化コバルト、酸化鉄、酸化銅、酸化マンガン、酸化クロム、酸化ニッケル、酸化スズ等の金属酸化物またはこれらの複合化合物を固溶させたものである。本発明による絵具は、薄膜形成を可能とするため、無機顔料の平均粒径は、小さい方がより薄層形成が可能である。好ましくは、１μｍ〜１０μｍが好ましい。特には、２μｍ〜９μｍである。
【００２４】
上記粒径の無機顔料を含む本発明の陶磁器用絵具を用いて、釉薬を塗布し乾燥した表面に彩色し焼成すると、無機顔料の粒子が釉薬表面上に均質な粒度で配列されることが可能である。従って、例えば、乾燥した釉薬の表面に本発明の陶磁器用絵具で、彩色し焼成すると、熔けたガラス層上の無機顔料が比重差によりガラス層に含浸され、表面成分の入れ替えが生じる結果釉薬層と絵具層が一体となって、光沢のある質感を有するガラス層が形成され得る。
【００２５】
従来、釉薬上に無機顔料を施した場合、顔料の薄膜の形成方法が難しく、厚みのコントロールが困難であった。一般に陶磁器顔料は、加熱処理がされることが前提であり、高温まで釉薬と反応せずかつ焼成による呈色変化を生じない条件に適合する特別に調整された酸化物や珪酸塩等を用いることから、着色剤のうち、顔料と比較して水や油に溶けない着色合成鉱物で構成されている。このため、顔料が厚くかかった場合、焼成後の釉薬表面がかさかさになったり、ブク、泡煮え等の現象が発生していた。本発明の陶磁器用絵具は、上記バインダーを用いることにより、上記の問題が発生せず、顔料の３０μｍ程度の薄膜形成が可能であり、この均一な薄層は、顔料層を透して下地の色が映り、微妙な色彩のぼかし表現を可能とする。
【００２６】
本発明に用いられるバインダーは、陶磁器に絵付けした後、焼成することより分解するが、その際、バインダーはフラッキス、あるいは釉薬の溶融中にカーボンとしての痕跡として残留して無機顔料の発色に影響を及ぼしたり、分解する際に発生するガスが有毒である等の問題がない範囲内で種々選択することができる。例えば、ポリウレタン樹脂、または、水溶性ポリエステル樹脂またはアクリル樹脂のエマルジョンが挙げられるが、好ましくは、ポリアルキレンオキシド系水溶性樹脂である。ポリアルキレンオキシド系水溶性樹脂は、焼成の際にほとんどが炭酸ガスと水になるため、カーボン残量が非常に少なくなり、色合いが良好である。ポリアルキレンオキシド系水溶性樹脂としては、特には水溶性ポリウレタン樹脂または水溶性ポリエステル樹脂である。
【００２７】
具体的には、本発明に用いられるポリアルキレンオキシド系水溶性樹脂は、ヒドロキシ基含有化合物と、多官能カルボン酸またはまたはその誘導体や多官能イソシアネートを反応して得られる、重量平均分子量１万以上の親水性高分子量化合物が好ましい。具体的には、エチレングリコール、プロピレングリコール、ポリエチレングリコール、ポリプロピレングリコール、ポリテトラメチレングリコール等のアルコール類とエチレンオキシド、プロピレンオキシド等を反応させたヒドロキシ基含有化合物、およびフタル酸、イソフタル酸、アジピン酸、フマル酸、マロン酸、マレイン酸、テレフタル酸、セバシン酸等のカルボン酸、トリレンジイソシアネート、ジフェニルメタンジイソシアネート、ヘキサメチレンジイソシアネート等イソシアネートが例示される多官能カルボン酸または多官能イソシアネートまたはそれらの誘導体とを反応させて得られる水溶性ポリエステル樹脂や水溶性ポリウレタン樹脂の親水性高分子量化合物である。
【００２８】
例えば、ポリエチレングリコールに４，４’−ジフェニルメタンジイソシアネートを反応させたポリウレタン樹脂、ポリエチレングリコールにイソホロンジイソシアネートを反応して得られたポリウレタン樹脂が挙げられる。
【００２９】
また、水溶性ポリエステル樹脂も用い得る。例えば、ポリオキシプロピレングリコールとテレフタル酸を縮合させたポリエステルが挙げられる。
【００３０】
バインダ−として、水とエマルジョンを形成するアクリル樹脂、あるいはポリ酢酸ビニルを用いることも考えられるが、エマルジョンは、その性質上粘性が低く、比重差の大きい無機顔料との混合物では、均質な分散状態を長時間保持することは困難である。また、アラビアゴムやデキストリン等の天然糊は、水による糊材溶解後、バクテリアの活性による腐敗が生じ、顔料の接着効果が減退する。また、カルボキシメチルセルロース等の高分子化学糊を用いると、経時的な粘性変化が激しいので、無機顔料精製工程で未反応酸化金属の洗浄処理に用いられた無機顔料中の残留酸との反応により、用いる顔料の選択によっては、再度の洗浄、ｐＨ調製を必要とする場合がある。また、乾燥後における保管時期の経過とともに空気中の湿度によるカビの発生がみられ、接着効果の減退が生じる等の問題がある。水溶性樹脂や水溶性ポリエステル系樹脂の場合、上記のような、バクテリアやカビの発生、接着効果の減少等の問題が非常に少ない。また、これらのバインダーを顔料と混合して得られた本発明の陶磁器用絵具は、素焼成形品や乾燥した釉薬塗布面、焼成した釉薬表面のいずれにも、筆運びが良好で、色の発色、艶に変化なく、彩色を自在に行うことができる。また、焼成後の顔料の定着が良好である。
【００３１】
本発明の陶磁器用絵具は、着色基材１００重量部に対し、水溶性バインダーを、特にはポリアルキレンオキシド系水溶性樹脂を、２０〜８０重量部を含むことが好ましい。特には、３０〜６０重量部含むことが好ましい。基本的には、水溶性バインダーの含有量が多い方が乾燥強度があがるが、含有比率が上がりすぎると着色基材の比率が低くなり発色の低下を招く。
【００３２】
本発明の陶磁器用絵具は、着色基材、水溶性バインダー、および水を混練し、用途に応じた粘度を有するエマルジョンの状態で、絵付けに用いることができる。スタンプ印刷、筆による絵付け等の用い方により、水分の配合割合を変化させて、用いるとよい。例えば、スタンプ印刷に用いる場合は、着色基材１００重量部に対し、水溶性バインダーを５０重量部とした場合、５０重量部〜１００重量部程度の水分量であってもよい。また、筆による絵付けの場合、彩色の技法により着色基材の濃さの適用があるが、例えば、着色基材１００重量部に対し、水溶性バインダーを５０重量部とした場合、８０重量部〜１６０重量部程度の水分量であってもよい。いずれの場合においても、着色が良好であり、自在で、繊細な彩色表現を可能とする。
【００３３】
しかし、時間経過とともに無機顔料の沈降分離が生じる。さらに、放置すると、上層ポリウレタン樹脂部に硬化現象が始まり膜層が形成される。攪拌すると均質化するが時間を要し、成分が不安定となるため固形状の形態が望ましい。また、絵付けを行う場合の絵具の濃淡を固形状の絵具を筆に含ませた水分で調整しうるため、繊細な絵付けを行う場合に固形状の絵具は適している。
【００３４】
固形状とするには、顔料、水溶性バインダー、および水を混練した後、型に入れて乾燥させる。固形状とすると、長時間の保存、保管が可能であるため好ましい。また、移動、運搬が容易であり、用いる場合は好みの濃さに水で溶解し調整すればよく、いずれの場所においても、陶磁器の絵付けが可能となる簡便性がある。
【００３５】
固形状の本発明の陶磁器用絵具は、小型容器に色彩別に分割収納すると、絵付けに際し、取り扱いが簡便である。適量の水分を含ませた筆を容器中の絵具に接触させることにより、必要な分量、必要な濃度の絵具を採取することができ、また、混色、重ね塗り等も容易にすることができる。型に入れ、固形化後容器に収納してもよいし、絵具が容器に流動性を有する時期に流しいれ、その後容器とともに、乾燥させて、固形状とする。使用後は、乾燥させれば、容器に残留している絵具は製造時の各成分の配合比が維持されることとなる。
【００３６】
固形状とする場合、溶解のために含有される水は放出させる必要があるが、乾燥時に亀裂が生じる等の商品性を損なわないよう、乾燥調製剤を添加することが好ましい。乾燥調整剤を水の代替として、または水と併用して添加することにより、容器に注入した練上絵具の乾燥速度を遅らせ、絵具の表面や容器周辺の偏った乾燥を避けることにより製品に亀裂の発生を防止することができる。加工性の観点から、水分量および、乾燥調整剤の粘度により好適な材料が選択される。乾燥調整剤としては、ポリエチレングリコールが好ましい。加工性に好ましい粘度の観点から、ポリエチレングリコールは、重量平均分子量２００程度が好ましい。ポリエチレングリコールの含量は、例えば、無機顔料１００重量部、水溶性樹脂５０重量部、ポリエチレングリコール５０重量部が好ましい。
【００３７】
本発明の他の態様としては、着色基材が、無機顔料と釉薬を混合したものである。釉薬を添加することにより、融点の低い釉薬層と本発明の絵具との焼成後の一体性が良好となり、焼成後の陶磁器の表面性が良好となる。顔料に添加する釉薬としては、光沢性を維持するために、フラッキス、透明釉薬等が挙げられる。また、絵具の質感や色彩のバリエーションのため、失透釉、マット釉、結晶釉、乳濁釉も用い得る。釉薬は、種々の無機化合物を組み合わせて調整するが、
ＳｉＯ２，Ａｌ２Ｏ３，Ｂ２Ｏ３，Ｐ２Ｏ５，ＣａＯ，ＭｇＯ，ＢａＯ，ＺｎＯ，ＰｂＯ，Ｎａ２Ｏ，Ｋ２Ｏ，Ｌｉ２Ｏ，Ｐ２Ｏ５等その他の酸化金属、炭酸塩金属との組み合わせである。環境や、人体への影響の観点から、鉛成分を含有しないことが好ましい。
【００３８】
これらの釉薬の選択、混合割合により、８００℃〜１３００℃程度の幅広い焼成温度設定に対応することができる。酸化焼成・還元焼成の選択、焼成温度の選択により、最終製品としての陶磁器の釉薬や陶磁器本来の色調の発現、風合いや表面性等が異なるため、焼成温度の設定は、陶磁器の製作者の重要な選択事項である。本発明の陶磁器用絵具は、このような製作者の要求に幅広く適応することができる。顔料の焼きつき等の問題がなく、種々の温度設定に適応することができ、下地の色や焼成温度が異なっても、焼成後の色調は一定であり、かつ、美しい色彩表現を可能とする陶磁器用絵具を提供し得る。
【００３９】
ここで、釉薬は、陶磁器顔料そのものの構成基材の耐火度と焼成温度との関連により、その種類および配合割合が選択され得る。たとえば、比較的低温の融点を有する釉薬を混合した場合、一旦高温焼成された釉薬表面に絵付け後、８００〜８５０℃の低温焼成が可能である。この場合は、本発明の絵具中に含まれる釉薬の含有量を多くすると、低温焼成にかかわらず顔料が均質に分散し良好に溶融する。例えば、含有量を８０重量％〜９０重量％とすることが好ましい。
【００４０】
また、比較的高温に融点を有する釉薬を混合した場合、絵付け後１１００℃〜１３００℃の高温焼成が可能である。この場合は、本発明の絵具に対する釉薬の含有量を比較的少なくすると、無機顔料の焼付きがなく良好である。例えば、含有量を１０重量％〜２０重量％とすることが好ましい。
【００４１】
本発明の絵具は、陶磁器の釉薬を施し焼成した後の表面に絵付けする上絵用絵具としても適用することができる。上絵用絵具は、▲１▼素地に絵具の濃淡をつけて描画表現をすることができる、▲２▼乾燥後塗り重ねができる、▲３▼部分消しを行うことで濃淡の表現をすることができるという、３つの要素を兼ね備えることが必要である。本願発明の絵具は上記の要件を満たし、美しい描画表現をすることが可能である。
【００４２】
さらに、本発明の陶磁器用絵具は、従来の絵付け方法を画期的に変えるものである。例えば、素焼された成形品の表面に、本発明の陶磁器用絵具を用いた絵付けを施した後、焼成する（本焼）工程からなる方法を提案する。本来素焼された成形品の表面は水分を吸収しやすい性質を有し、この表面に絵付けした場合、従来の絵具であれば、絵具に含まれる水分が素焼成形品の表面に吸収されて、顔料のみが表面に残留し、細線、ぼかし、色の重ね塗り等の繊細な技法が充分生かせなかった。本発明の陶磁器用絵具を用いた絵付けを素焼成形品に行うと、水分の素焼表面への吸着がなく、円滑に筆を運ぶことができ、繊細な色彩表現を可能とする。また、素焼成形品の有する色にも影響を受けることなく、一定の色調を保持することができる。さらに、本発明の陶磁器用絵具は、釉薬を含む場合、絵付け後に釉薬を施さなくても、焼成後、剥離しにくい艶のある表面層を形成する。
【００４３】
また、素焼成形品に、釉薬を塗布する工程、塗布乾燥した釉薬の表面に本発明の陶磁器用絵具を用いて絵付けを行う工程、その後焼成する（本焼）工程からなる方法により、陶磁器を製造することができる。この場合、釉薬は塗布後乾燥してから焼成し、その上に絵付けを行いさらに焼成を行ってもよい。また、素焼成形品に絵具の絵付けを行い、彩色を施した部分を除いた残部に釉薬を施し、焼成を行ってもよい。さらに、素焼成形品に本発明の陶磁器用絵具で絵付けを行った後、その上に釉薬を塗布し乾燥後、本焼することも可能である。
【００４４】
本発明の上記いずれによる方法においても、加熱工程を本焼１度ですますことができる。さらに、絵付け工程において、微妙な色彩の変化、ぼかし、濃淡、マット感、色の塗り重ね等の多彩な表現調整が自在にできる。
【００４５】
以上、本発明について説明したが、本発明は、これらの実施の態様のみに限定されるものではなく、その趣旨を逸脱しない範囲内で、当業者の知識に基づき、種々なる改良、変更、修正を加えた態様で実施しうるものである。
【００４６】
【実施例】
次に、本発明にかかる本焼絵具の実施の形態を以下の実施例により詳しく説明する。
【００４７】
なお、実施例中、「％」とあるのは、重量％を示す。「部」とあるのは、重量部を示す。
【００４８】
（水溶性バインダーの製造例１）
ポリオキシエチレンオキシプロピレングリコール（ＥＯ含量８５％、平均重量分子量１００００）にテレフタル酸で縮合して得た重量平均分子量１１００００の水溶性ポリエステル樹脂を水に溶解して３０重量％水溶液を得た。
【００４９】
（水溶性バインダーの製造例２）
エチレングリコール（重量平均分子量４１００）１００部にトルエン溶媒中でイソホロンジイソシアネート５．４部を反応して得た重量平均分子量１５００００の水溶性ポリウレタン樹脂で、その後トルエンを水４０重量％で置換したものを得た。
【００５０】
（水溶性バインダーの製造例３）
ポリエチレングリコール（重量平均分子量８５００）１００部に４，４’−ジフェニルメタンジイソシアネート２．８部（ＯＨ／ＮＣＯ＝１．０４）を反応させて得られた重量平均分子量８００００の水溶性ポリウレタン樹脂を得た。これを水に溶解し、３０重量％水溶液とした。
【００５１】
（着色基材）
Ｚｒ−Ｓｉ−Ｖ系で平均粒径２μｍの青顔料９０重量部に対し、上記製造例で製造した水溶性ポリウレタン樹脂またはポリエチレングリコールにて混合し固形状にした無機顔料を用いた。
【００５２】
（素焼成形品）
３重量％程度のＦｅ２Ｏ３を含む唐津土の含鉄粘土を用い、予め８００℃で素焼を行った。この素焼成型品は、非常にポーラスな素地表面を有しているため吸水性が高い。また、３重量％程度のＦｅ２Ｏ３を含む唐津土の含鉄粘土を用いているため、素地が茶色を呈している。通常、０．３重量％以下のＦｅ２Ｏ３を含む陶土を用いれば、酸化焼成、還元焼成において素地そのものが比較的白く焼き上がるため、顔料の発色は鮮やかであると想定されるが、本実施例においては、上記の鉄含有量の多い陶土をあえて選択し、表面性が彩色に与える影響および、素描顔料下の素地色が顔料の発色に与える影響について、観察した。
【００５３】
（釉薬）
素焼製品の上に施す釉薬は、石灰亜鉛系の象牙色釉薬とした。
石灰亜鉛系の象牙色釉薬は、信楽長石６０重量％、石灰石１８重量％、カオリン１０重量％、鳥屋根硅石１２重量％、酸化亜鉛６重量％、珪酸ジルコニウム８重量％の基礎釉薬に対して、Ｖ−Ｚｒ系黄顔料を２重量％添加し湿式粉砕をしたものを用いた。
【００５４】
（実施例１）
製造例１で製造した水溶性ポリエステル樹脂を、着色基材１００重量部に対し５重量部〜８０重量部の範囲で混合して本発明の陶磁器用絵具を調製し、水を毛筆による絵具の伸びの状態を観察した。
結果を表１に示す。
【００５５】
【表１】
（実施例２）
製造例２で製造した水溶性ポリウレタン樹脂を、着色基材１００重量部に対し、５０重量部とし、水の配合割合を変化させて、本発明の陶磁器用絵具を調製し、素焼成形品に釉薬を塗布し乾燥した表面に、シリコンゴム製、合成樹脂製、スポンジ製の３種のスタンプ型に絵具を含ませてスタンプ印刷を行った。結果を表２に示す。これらを、１２３０℃で焼成した。着色が鮮やかで、美しい仕上がりであった。
【００５７】
【表２】
（実施例３）
上記製造例３で製造した水溶性ポリウレタン樹脂を、着色基材１００重量部に対し、５０重量部とし、水の配合割合を変化させて、本発明の陶磁器用絵具を調製し、素焼成形品に釉薬を塗布し乾燥した表面に用い筆塗り絵付けに適した水分量を観察した。結果を表３に示す。これらを、１２３０℃で焼成した。着色が鮮やかで、美しい仕上がりであった。
【００５９】
【表３】
（実施例４）
本発明の固形状の陶磁器用絵具を製造した。
着色基材 ：１００重量部
製造例１で製造したポリエステル樹脂： ５０重量部
ポリエチレングリコール（♯２００）： ５０重量部
上記の割合で材料を準備し、陶器製の乳鉢容器と乳棒から構成される石川式ライカイ機で混合し（回転数；３０回／分、１５分間）、内径３３ｍｍ×高さ１５ｍｍの円筒状小型陶器に２０ｇ充填し、遠赤外線乾燥炉の中で６０℃の温度にて２０時間乾燥を行い固形化した。
これを、（実施例４−１）素焼成形品の表面、（実施例４−２）素焼成形品の表面に釉薬を塗布し乾燥した表面、（実施例４−３）素焼成形品の表面に釉薬を塗布し１３００℃で焼成した表面に絵付けを施した。
絵付け後、それぞれ（実施例４−１）１２３０℃、（実施例４−２）１２３０℃、（実施例４−３）８３０℃で焼成した。着色が鮮やかで、美しい仕上がりであった。
【００６１】
（実施例５）
上絵用絵具（ホウ酸−鉛−アルミナ−シリカ系のフラックス９０部、無機顔料１０部を添加し混合粉砕し調整した）： １００部
製造例２で製造した水溶性ポリウレタン樹脂： ５０部
水 ：上記の上絵用絵具と水溶性ポリウレタン樹脂に、１００部、１１０部、１２０部、１３０部をそれぞれ添加した。
上記４種の配合のサンプルを用意し、筆塗りにて多重絵付けした。絵付け品は、２４時間乾燥後、８２０℃で焼成した。
その結果、絵具飛びや絵具剥離が見られず、表面性よく焼きあがった。
【００６２】
本発明にかかる絵具は、上絵用絵具にも、好適に用いることができることがわかる。
【００６３】
（実施例６）
無機顔料： １０重量％
釉薬Ａ（ノリタケカンパニ−製の耐酸性上絵具用３７８００シリーズのフラッキス）： ９０重量％
の配合の着色基材１００重量部に対し、製造例３で製造した水溶性ポリウレタン樹脂（固形分として）３０重量部を混合して本発明の陶磁器用絵具を調整した。上記調製した、本発明にかかる絵具で素焼製品に釉薬を塗布、乾燥後の表面に、絵付けを行った。８２０℃〜８５０℃で焼成した。顔料は均質に溶融し所望の発色を得ることができた。
【００６４】
（実施例７）
無機顔料 ７０重量％
釉薬Ｂ： ３０重量％
の配合の着色基材１００重量部に対し、製造例１で製造した水溶性ポリエステル樹脂（固形分として）３０重量部を混合して本発明の陶磁器用絵具を調整した。釉薬Ｂは、以下の割合で混合して調整した。
平津長石 ５０重量％ 石灰石 １０重量％
カオリン１０重量％ 硅石 ３０重量％
素焼製品に釉薬を塗布し乾燥後の表面に、上記調製した本発明にかかる絵具で絵付けを行った。１２５０℃〜１３００℃で焼成した。
顔料は均質に溶融し所望の発色を得ることができた。
【００６５】
（実施例８）
（呈色試験）
白系 Ｚｒ−Ｓｉ系の１色を含めた、ピンク系１色（Ａｌ−Ｍｎ系）、赤系２色（Ｓｅ−Ｃｄ−Ｚｒ系）、黄系１色（Ｖ−Ｓｎ系）、ヒワ系２色（Ｓｎ−Ｚｒ−Ｓｉ−Ｖ系）、グリン系１色（Ｃｏ−Ｃｒ−Ａｌ−Ｚｎ系）、ブルー系４色（Ｃｏ−Ｚｎ−Ａｌ系、Ｚｒ−Ｓｉ−Ｖ系）、茶系２色（Ｚｎ−Ａｌ−Ｆｅ−Ｃｒ系）、黒系１色（Ｆｅ−Ｃｏ−Ｃｒ系）、紫系３色（Ａｌ−Ｍｎ−Ｃｏ系）、グレー系１色（Ｚｒ−Ｓｉ−Ｃｏ−Ｎｉ系）の計２０色を用い、着色基材とし、実施例６，７と同様の方法で、本発明の陶磁器用絵具を製造し、石灰亜鉛系象牙色釉薬を塗布乾燥した表面に、これらによる彩色を施し、焼成して呈色試験を行った。
焼成は、１２３０℃で、酸化焼成および還元焼成を行った。いずれの焼成法によっても、安定した発色が得られた。
【００６６】
（実施例９）
（発生ガス、残渣の試験）
本発明の陶磁器用絵具で、絵付けを行った後、８５０℃で４時間焼成し、分解ガスの有無を調べた。青酸系ガスは全く検知されず、一酸化炭素の発生は認められなかった。
【００６７】
【実施例１０】
（素地彩色）
上記素焼成形品の表面に、顔料１（Ｖ−Ｓｎ系の黄）、顔料２（Ｆｅ−Ｃｏ−Ｃｒ系の黒）、および顔料３（Ａｌ−Ｍｎ系のピンク）で素地彩色を行った。電気炉１２３０℃で還元焼成を行った。
その結果、ポーラスな表面であるにも関わらず、顔料が表面に吸収されず、筆をとられず円滑に彩色し、濃淡自在に絵付けを行うことができた。また、素地色が彩色に影響することなく、絵の具の発色は良好であった。その結果、彩色に多彩な表現方法が可能となり、制作者の作風が活かされ、美的価値を高める効果を得ることができた。
【００６８】
【発明の効果】
本発明にかかる陶磁器用絵具は、以下のような効果を有する。
（１）素焼成形品の表面に、または、これに施釉乾燥の後釉薬上に、さらには、釉薬焼成後その上に、筆塗り、スタンプ印刷を行う場合、糊材添加等の釉薬表面の前処理の必要なく、自在に彩色できる。
（２）絵付けに際し、釉薬上に描くため、下地の釉薬色にとらわれることなく、下地釉薬との色調合により、自由な着彩作業が可能である。
（３）下地釉薬の透明、有色に影響されず、美しく、同一の色の再現ができる。
（４）釉薬上に３０μｍという薄膜にて描写が可能であるため、色の濃淡や、ぼかしが可能である。
（５）素焼の材料に、本発明の絵具を施すという、新たな絵付け方法を提示する。
（６）加工工程の省略、特に加熱工程を本焼１回のみで上絵付け効果を奏することができ、コスト上、製造工程の所要時間を大幅に短縮することができる。
（７）小ロットの絵具の製造にも対応することができ、使用の用途に応じて、種々の配合割合を選択することができることから、プリントによる絵付けを行うような大量生産品にはない、筆のタッチを含めた色彩表現を主とする陶磁器の製作現場において、有用に用い得る。
（８）固形状陶磁器用絵具、また、絵付けの層厚との関連で、種々の粘度を有する液状絵具の製造も可能であり、水溶性であり、油性のメディウムを絵付けの際その都度配合して使用する繁雑さがなく、水に好みの濃淡に溶かすだけという簡便な取扱いで、工芸的付加価値を高めることができ、新たな表現方法を開拓することが可能である。
（９）固形状とした場合、バインダーと顔料の均一な配合割合を最後まで、保持することが可能であり、長期間にわたり、品質を維持することができる。
（１０） 備前焼等の、釉薬を用いず、材料の土の焼色や風合い、炎色や薪による模様の発現を持ち味としていた、陶器の製造工程において、本発明による陶磁器用絵具による多彩かつ繊細な表現を付加することにより、新たな創作の表現を期待できる。
（１１） 酸化焼成、還元焼成いずれにおいても、また焼成温度によらず、安定した発色が得られる。
（１２） 使用、焼成に際し、臭いもなく、環境ホルモンに影響する可能性は非常に少ない。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a novel ceramic paint and a method of using the ceramic paint, and more particularly to a ceramic paint that is easy to handle and enables a new coloring expression, and a method of using the ceramic paint using the same.
[0002]
Problems to be solved by the prior art and the invention
2. Description of the Related Art Conventionally, manufacturing processes for Japanese and Western tableware, decorative articles, and the like basically include a raw material processing step, a forming step, a drying step, and a firing step. Generally, unfired molded articles are unfired. After unglazing, it is glazed and fired. Conventionally, when painting is applied to the surface of the ceramic, an undercoat is applied to the dried cloth after the glaze, and a transparent glaze is applied, followed by firing. When overpainting is performed on top of it, it is painted and then baked to obtain a product. When painting on the surface of the dried glaze, the glaze surface is in a state where the glaze powder is wiped all over the surface, and the glaze of the paint brush is covered with powdery glaze, hindering the smooth carrying of the brush, I couldn't make a delicate expression using a fine brush. In addition, there is a problem that the glaze is loosened due to the moisture of the paint at the time of painting, and is mixed with the paint, or the surface property of the glaze is impaired.
[0003]
In addition, when painting on a dry glaze, an improvement has been made to fix the glaze surface so that the powder on the glaze surface does not affect the painting process. Specifically, a method has been proposed in which a binder such as a resin is added to glaze to form a resin film on the surface (for example, Patent Document 1). Patent Document 1 discloses that after a primer mainly composed of a synthetic resin emulsion or a water-soluble polymer, or a mixture thereof is applied to the surface of a raw glaze layer, a pattern for transfer is closely adhered, and aging of the glaze and firing of the pattern layer are performed. At the same time.
[0004]
However, although the heat treatment step is simplified to one time by the above method, there is a possibility that the glaze layer may be damaged because a polymer aqueous solution containing much water, that is, a primer is applied on the raw glaze.
[0005]
Also, a method has been proposed in which a glaze and a primer treatment are combined into a single process using a composition containing a water-based resin emulsion having good adhesion to the picture layer and high water resistance, and using a composition containing a surfactant. (For example, Patent Document 2).
[0006]
However, the resin contained in the glaze may be decomposed by heating to generate a harmful gas, or carbonized during firing, with traces of the resin affecting painting.
[0007]
Alternatively, there is a method in which the unglazed dough is glazed, dried and baked, then painted using China paint, which is then painted, and further baked. In conventional paints, the color of the underlayer affects the final color development through the pigment. In the case of transparent glaze, the color of the ceramic material, and in the case of coloring the glaze, the color of the coloring paint depends on the color of the colored glaze. For this reason, it is necessary to calculate this and apply coloring, and as a result of mixing with the base color, the developed color lacks vividness. Therefore, in order to make the color shine, it has been required that the ceramic material has a milky white color that is closer to white, and that the glaze has a color close to white.
[0008]
In the painting method using China paint, painting is usually performed while kneading the pigment and the oil-based medium on a pallet, but the mixing ratio of the pigment and the medium must be changed each time it is used. Further, the used brush must be washed with turpentine oil each time, and there are problems that the smell of the oily solvent fills the periphery of the work place and that the brush is severely damaged. Furthermore, paints are easy to solidify and are difficult to handle.In addition, paints in tubes suffer from problems such as separation of components in the tubes, and pigments solidifying in the tubes with aging. there were.
[0009]
In addition, there is a painting method in which a paint is applied to the unfired base material, and the resultant is baked with a transparent glaze. In this case, the water absorption of the paint is absorbed by the water absorption of the unglazed base itself, so that the movement and movement of the brush are restricted, and it is impossible to draw a stretchy touch or delicate fine lines without skill.
[0010]
[Problems to be solved by the invention]
The present inventors have solved the above-mentioned various problems in the ceramic manufacturing method which has been conventionally performed, can handle the ceramics easily, can simplify the manufacturing process of the ceramics, can reduce the cost, and can realize a more delicate expression. The present invention was completed as a result of intensive research with the aim of developing a new ceramic paint.
[0011]
[Patent Document 1]
JP-A-54-81316
[Patent Document 2]
Japanese Patent Publication No. 7-45351
[0012]
[Means for Solving the Problems]
The ceramic paint of the present invention contains at least a colored base material and a water-soluble binder, and the water-soluble binder is a polyalkylene oxide-based water-soluble resin.
[0013]
The ceramic paint of the present invention may contain 20 to 80 parts by weight of a polyalkylene oxide-based water-soluble resin based on 100 parts by weight of a colored base material. In particular, it may contain 30 to 60 parts by weight of a polyalkylene oxide-based water-soluble resin based on 100 parts by weight of the coloring base material.
[0014]
Here, the colored base material contains an inorganic pigment, and the inorganic pigment is a solid solution of a combination of one selected from the group consisting of silica, alumina, and a composite of silica and alumina and a metal oxide. is there.
[0015]
The inorganic pigment may have a particle size of 1 μm to 10 μm.
[0016]
Here, the polyalkylene oxide-based water-soluble resin is a hydrophilic high molecular weight compound having a weight average molecular weight of 10,000 or more, obtained by reacting a hydroxy group-containing compound with a polyfunctional isocyanate or a polyfunctional carboxylic acid or a derivative thereof. Can be
[0017]
Another embodiment of the ceramic paint of the present invention may be a solid containing a pigment, a polyalkylene oxide-based water-soluble resin, and a drying regulator.
[0018]
Here, the drying regulator may be polyethylene glycol.
[0019]
Further, the coloring substrate may include an inorganic pigment and a glaze.
[0020]
The ceramics of the present invention can be colored using any of the ceramic paints described above.
[0021]
In addition, the method for manufacturing a ceramic according to the present invention includes a step of preparing an unfired shaped article,
A step of painting the surface of the unbaked shaped article using the ceramic paint according to any of the above,
Baking step.
[0022]
BEST MODE FOR CARRYING OUT THE INVENTION
The ceramic paint according to the present invention includes a pigment and a binder, wherein the binder is a polyalkylene oxide-based water-soluble resin. The ceramic paint of the present invention can change the concentration of the pigment arbitrarily by water, even on the surface of a dried glaze, the surface of a calcined glaze, or the surface of an unbaked molded product. A vivid and constant color tone can be exhibited without being affected by the colors of the respective bases.
[0023]
The coloring substrate used in the present invention may include an inorganic pigment. The inorganic pigment is a solid solution of metal oxides such as cobalt oxide, iron oxide, copper oxide, manganese oxide, chromium oxide, nickel oxide, tin oxide, or a composite compound of these in silica, alumina, or a composite of silica and alumina. It was made. Since the paint according to the present invention can form a thin film, the smaller the average particle size of the inorganic pigment is, the more a thin layer can be formed. Preferably, it is 1 μm to 10 μm. In particular, it is 2 μm to 9 μm.
[0024]
Using the ceramic paint of the present invention containing an inorganic pigment having the above particle size, applying a glaze to the dried surface and coloring and firing the same, the particles of the inorganic pigment can be arranged with a uniform particle size on the glaze surface. It is. Therefore, for example, when the surface of a dried glaze is painted and baked with the ceramic paint of the present invention, the inorganic pigment on the molten glass layer is impregnated into the glass layer due to a difference in specific gravity, and the surface components are exchanged. And the paint layer may be integrated to form a glass layer having a glossy texture.
[0025]
Conventionally, when an inorganic pigment is applied on a glaze, it is difficult to form a thin film of the pigment, and it is difficult to control the thickness. Generally, ceramic pigments are premised on being subjected to heat treatment, and use specially adjusted oxides or silicates that meet the conditions that do not react with the glaze up to high temperatures and do not cause color change due to firing Therefore, among the coloring agents, the coloring agent is composed of a colored synthetic mineral that is insoluble in water and oil as compared with the pigment. For this reason, when the pigment is thick, the surface of the glaze after firing becomes bulky, and there are phenomena such as bubbling and bubbling. By using the binder, the ceramic paint of the present invention does not have the above-mentioned problems, and can form a thin film of about 30 μm of the pigment. Colors are reflected, enabling subtle color blur expression.
[0026]
The binder used in the present invention is decomposed by firing after painting on ceramics, but at that time, the binder remains as a trace as carbon during melting of the glaze or glaze, affecting the color development of the inorganic pigment. And various gases can be selected within a range that does not cause a problem such as that the gas generated upon decomposition is toxic. For example, a polyurethane resin, or an emulsion of a water-soluble polyester resin or an acrylic resin can be used, and a polyalkylene oxide-based water-soluble resin is preferable. Most of the polyalkylene oxide-based water-soluble resin is converted into carbon dioxide gas and water at the time of firing, so that the remaining amount of carbon is very small and the color tone is good. The polyalkylene oxide-based water-soluble resin is particularly a water-soluble polyurethane resin or a water-soluble polyester resin.
[0027]
Specifically, the water-soluble polyalkylene oxide resin used in the present invention is obtained by reacting a hydroxy group-containing compound with a polyfunctional carboxylic acid or a derivative thereof or a polyfunctional isocyanate, and has a weight average molecular weight of 10,000 or more. Are preferred. Specifically, ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, a hydroxy group-containing compound obtained by reacting an alcohol such as polytetramethylene glycol with ethylene oxide, propylene oxide and the like, and phthalic acid, isophthalic acid, adipic acid, Reaction with carboxylic acids such as fumaric acid, malonic acid, maleic acid, terephthalic acid, and sebacic acid, and polyfunctional carboxylic acids or polyfunctional isocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, and hexamethylene diisocyanate, or derivatives thereof. It is a hydrophilic high molecular weight compound of a water-soluble polyester resin or a water-soluble polyurethane resin obtained by the reaction.
[0028]
For example, a polyurethane resin obtained by reacting polyethylene glycol with 4,4′-diphenylmethane diisocyanate, and a polyurethane resin obtained by reacting polyethylene glycol with isophorone diisocyanate are exemplified.
[0029]
Further, a water-soluble polyester resin may be used. For example, polyester obtained by condensing polyoxypropylene glycol and terephthalic acid can be used.
[0030]
As the binder, it is conceivable to use an acrylic resin or a polyvinyl acetate which forms an emulsion with water, but the emulsion has a low viscosity due to its nature and, when mixed with an inorganic pigment having a large specific gravity difference, a homogeneous dispersion state is required. Is difficult to maintain for a long time. Natural glue such as gum arabic or dextrin, after dissolving the glue material with water, rots due to the activity of bacteria, and the adhesive effect of the pigment is reduced. In addition, when using a high-molecular-weight chemical glue such as carboxymethyl cellulose, the viscosity changes over time are severe, so the reaction with the residual acid in the inorganic pigment used in the washing treatment of the unreacted metal oxide in the inorganic pigment refining step, Depending on the selection of the pigment to be used, washing and pH adjustment may be required again. Further, as storage time elapses after drying, mold is generated due to humidity in the air, and there is a problem that the adhesive effect is reduced. In the case of a water-soluble resin or a water-soluble polyester-based resin, there are very few problems such as the occurrence of bacteria and mold and a decrease in the adhesive effect as described above. In addition, the ceramic paints of the present invention obtained by mixing these binders with pigments have good brushability and color development on any of the unbaked shaped products, the dried glaze-coated surface, and the fired glaze surface. Coloring can be performed freely without changing gloss. Also, the fixation of the pigment after firing is good.
[0031]
The ceramic paint of the present invention preferably contains 20 to 80 parts by weight of a water-soluble binder, particularly a polyalkylene oxide-based water-soluble resin, based on 100 parts by weight of the coloring base material. In particular, it is preferable to contain 30 to 60 parts by weight. Basically, the higher the content of the water-soluble binder, the higher the drying strength. However, if the content ratio is too high, the ratio of the colored base material becomes low, and the color development is reduced.
[0032]
The ceramic paint of the present invention can be used for painting by kneading a coloring base material, a water-soluble binder, and water, and in an emulsion state having a viscosity according to the intended use. It is preferable to change the mixing ratio of water depending on how to use stamp printing, painting with a brush, or the like. For example, when used for stamp printing, the water content may be about 50 to 100 parts by weight when the water-soluble binder is 50 parts by weight with respect to 100 parts by weight of the colored base material. Further, in the case of painting with a brush, there is an application of the density of the colored base material by a coloring technique. For example, when the water-soluble binder is 50 parts by weight with respect to 100 parts by weight of the colored base material, 80 parts by weight is used. The water content may be about 160 parts by weight. In any case, coloring is favorable, and free and delicate coloring can be expressed.
[0033]
However, sedimentation of the inorganic pigment occurs over time. Further, when left to stand, a curing phenomenon starts in the upper polyurethane resin portion to form a film layer. When the mixture is agitated, the mixture is homogenized, but it takes time, and the components become unstable. Therefore, a solid form is desirable. In addition, since the density of the paint for painting can be adjusted by the water content of the brush in the solid paint, the solid paint is suitable for delicate painting.
[0034]
To obtain a solid, a pigment, a water-soluble binder, and water are kneaded, then put in a mold and dried. The solid form is preferable because it can be stored and stored for a long time. Further, it is easy to move and transport, and when used, it may be adjusted by dissolving it with water to a desired concentration, and there is simplicity that ceramics can be painted in any place.
[0035]
If the solid ceramic paint of the present invention is divided and stored in a small container for each color, it is easy to handle when painting. By bringing a brush containing an appropriate amount of water into contact with the paint in the container, it is possible to collect a necessary amount of paint and a necessary concentration of the paint, and it is also possible to easily perform color mixing, overpainting and the like. It may be put in a mold and then stored in a container after solidification, or it may be poured when the paint has fluidity in the container, and then dried together with the container to a solid state. After use, if dried, the paint remaining in the container will maintain the compounding ratio of each component at the time of manufacture.
[0036]
In the case of a solid form, the water contained for dissolution must be released, but it is preferable to add a dry preparation so as not to impair the commercial properties such as cracks during drying. Addition of a drying regulator as a substitute for water or in combination with water slows down the drying speed of the mixed paint poured into the container and avoids uneven drying of the paint surface and around the container, resulting in cracks in the product. Can be prevented from occurring. From the viewpoint of processability, a suitable material is selected according to the amount of water and the viscosity of the drying regulator. As the drying regulator, polyethylene glycol is preferred. From the viewpoint of preferable viscosity for processability, polyethylene glycol preferably has a weight average molecular weight of about 200. The content of polyethylene glycol is preferably, for example, 100 parts by weight of an inorganic pigment, 50 parts by weight of a water-soluble resin, and 50 parts by weight of polyethylene glycol.
[0037]
In another embodiment of the present invention, the coloring substrate is a mixture of an inorganic pigment and a glaze. By adding the glaze, the glaze layer having a low melting point and the paint of the present invention have good integrity after firing, and the fired ceramics have good surface properties. The glaze to be added to the pigment includes, for example, a flax and a transparent glaze in order to maintain glossiness. In addition, devitrified glazes, matt glazes, crystal glazes, and emulsion glazes may be used for variations in the texture and color of the paint. Glaze is adjusted by combining various inorganic compounds,
SiO 2 , Al 2 O 3 , B 2 O 3 , P 2 O 5 , CaO, MgO, BaO, ZnO, PbO, Na 2 O, K 2 O, Li 2 O, P 2 O 5 Etc. in combination with other metal oxides and carbonate metals. From the viewpoint of the influence on the environment and the human body, it is preferable that the lead component is not contained.
[0038]
Depending on the selection and mixing ratio of these glazes, it is possible to cope with a wide range of firing temperature settings of about 800 ° C. to 1300 ° C. Depending on the choice of oxidizing firing, reduction firing, and firing temperature, the glaze of ceramic as final product, the expression of the original color tone of the ceramic, the texture and the surface properties, etc., differ, so the setting of the firing temperature is important for the ceramic manufacturer. Choices. The ceramic paint of the present invention can widely adapt to such a demand of the maker. There is no problem such as burn-in of the pigment, and it can be adapted to various temperature settings, and even if the base color and firing temperature are different, the color tone after firing is constant and beautiful color expression is possible. Ceramic paints may be provided.
[0039]
Here, the type and the mixing ratio of the glaze can be selected depending on the relationship between the fire resistance of the constituent base material of the ceramic pigment itself and the firing temperature. For example, when a glaze having a relatively low melting point is mixed, low-temperature firing at 800 to 850 ° C. is possible after painting the glaze surface once fired at a high temperature. In this case, when the content of the glaze contained in the paint of the present invention is increased, the pigment is uniformly dispersed and melted well regardless of the low-temperature firing. For example, the content is preferably set to 80% by weight to 90% by weight.
[0040]
When a glaze having a melting point at a relatively high temperature is mixed, firing at a high temperature of 1100 ° C. to 1300 ° C. after painting is possible. In this case, when the content of the glaze in the paint of the present invention is relatively small, there is no seizure of the inorganic pigment and good. For example, the content is preferably set to 10% by weight to 20% by weight.
[0041]
The paint of the present invention can also be applied as an overpaint for painting a surface after applying a glaze of ceramic and firing. Top paints can be expressed as: (1) the shade of the paint can be applied to the base material for drawing expression; (2) overpainting after drying; and (3) shading by performing partial erase. It is necessary to combine the three elements that can be performed. The paint of the present invention satisfies the above-mentioned requirements and is capable of producing a beautiful drawing expression.
[0042]
Further, the ceramic paint of the present invention is a revolutionary modification of the conventional painting method. For example, a method is proposed in which the surface of the unfired molded article is painted using the ceramic paint of the present invention and then fired (main firing). Originally, the surface of the unbaked molded article has the property of easily absorbing moisture, and when painting on this surface, if it is a conventional paint, the moisture contained in the paint is absorbed by the surface of the unbaked molded article, Only the pigment remained on the surface, and delicate techniques such as fine lines, blurring, and overcoating of colors could not be fully utilized. When the painting using the ceramic paint of the present invention is applied to the unfired shaped article, the brush can be smoothly carried without absorbing moisture to the unfired surface, and delicate color expression can be achieved. In addition, a constant color tone can be maintained without being affected by the color of the fired shaped product. Further, when the ceramic paint of the present invention contains a glaze, it forms a glossy surface layer that is difficult to peel off after firing even if the glaze is not applied after painting.
[0043]
In addition, a method of applying a glaze to the unbaked shaped article, a step of painting the surface of the applied and dried glaze using the ceramic paint of the present invention, and a subsequent firing (main firing) step is used to prepare the ceramic. Can be manufactured. In this case, the glaze may be dried after application and fired, and then painted and further fired. Alternatively, the unbaked shaped article may be painted with paint, glaze may be applied to the remaining part except for the colored part, and firing may be performed. Further, it is also possible to apply a glaze to the unbaked shaped article after painting it with the ceramic paint of the present invention, dry it, and then bake it.
[0044]
In any of the above-mentioned methods of the present invention, the heating step can be carried out once in the final firing. Furthermore, in the painting process, a variety of expression adjustments such as subtle color changes, blurs, shades, matte feelings, and overpainting of colors can be freely performed.
[0045]
Although the present invention has been described above, the present invention is not limited to only these embodiments, and various improvements, changes, and modifications may be made based on the knowledge of those skilled in the art without departing from the spirit of the present invention. Can be implemented.
[0046]
【Example】
Next, an embodiment of the present firing paint according to the present invention will be described in detail by the following examples.
[0047]
In Examples, "%" indicates% by weight. "Parts" indicates parts by weight.
[0048]
(Production example 1 of water-soluble binder)
A water-soluble polyester resin having a weight average molecular weight of 110,000 obtained by condensing polyoxyethyleneoxypropylene glycol (EO content: 85%, average weight molecular weight: 10,000) with terephthalic acid was dissolved in water to obtain a 30% by weight aqueous solution.
[0049]
(Production Example 2 of water-soluble binder)
A water-soluble polyurethane resin having a weight average molecular weight of 150,000 obtained by reacting 5.4 parts of isophorone diisocyanate with 100 parts of ethylene glycol (weight average molecular weight of 4100) in a toluene solvent, and then replacing toluene with 40% by weight of water. Obtained.
[0050]
(Production Example 3 of water-soluble binder)
100 parts of polyethylene glycol (weight average molecular weight 8500) was reacted with 2.8 parts of 4,4'-diphenylmethane diisocyanate (OH / NCO = 1.04) to obtain a water-soluble polyurethane resin having a weight average molecular weight of 80,000. . This was dissolved in water to obtain a 30% by weight aqueous solution.
[0051]
(Colored substrate)
An inorganic pigment obtained by mixing with the water-soluble polyurethane resin or polyethylene glycol produced in the above production example to 90 parts by weight of a Zr-Si-V-based blue pigment having an average particle size of 2 μm and solidified was used.
[0052]
(Unfired product)
About 3% by weight of Fe 2 O 3 Was preliminarily sintered at 800 ° C. using the iron-containing clay of Karatsu earth containing. This fired element has a very porous substrate surface and therefore has a high water absorption. Also, about 3% by weight of Fe 2 O 3 The base color is brown because of the use of Karatsu clay containing iron. Usually, less than 0.3% by weight of Fe 2 O 3 In the case of using porcelain clay containing, since the base itself is baked relatively white in oxidation firing and reduction firing, the color development of the pigment is assumed to be vivid. The effect of the surface properties on the coloring and the effect of the background color under the drawing pigment on the color development of the pigment were observed.
[0053]
(glaze)
The glazing applied to the unglazed product was a lime-zinc ivory glaze.
The lime zinc based ivory glaze is based on Shigaraki feldspar 60% by weight, limestone 18% by weight, kaolin 10% by weight, bird roof silica stone 12% by weight, zinc oxide 6% by weight, zirconium silicate 8% by weight base glaze, 2% by weight of a V-Zr-based yellow pigment was added and wet-pulverized.
[0054]
(Example 1)
The water-soluble polyester resin produced in Production Example 1 was mixed in a range of 5 parts by weight to 80 parts by weight with respect to 100 parts by weight of the coloring base material to prepare a ceramic paint of the present invention, and water was applied to the paint to extend the brush. Was observed.
Table 1 shows the results.
[0055]
[Table 1]
(Example 2)
The water-soluble polyurethane resin produced in Production Example 2 was used in an amount of 50 parts by weight with respect to 100 parts by weight of the coloring base material, and the mixing ratio of water was changed to prepare the ceramic paint of the present invention. Was applied and dried, and stamp printing was performed using three types of stamps made of silicone rubber, synthetic resin, and sponge with paints. Table 2 shows the results. These were fired at 1230 ° C. The coloring was vivid and beautiful.
[0057]
[Table 2]
(Example 3)
The water-soluble polyurethane resin produced in Production Example 3 was used in an amount of 50 parts by weight with respect to 100 parts by weight of the coloring substrate, and the mixing ratio of water was changed to prepare the ceramic paint of the present invention. The glaze was applied to the dried surface and the amount of water suitable for brush painting was observed. Table 3 shows the results. These were fired at 1230 ° C. The coloring was vivid and beautiful.
[0059]
[Table 3]
(Example 4)
A solid ceramic paint of the present invention was manufactured.
Colored substrate: 100 parts by weight
Polyester resin produced in Production Example 1: 50 parts by weight
Polyethylene glycol ($ 200): 50 parts by weight
The materials were prepared in the above ratios and mixed with an Ishikawa-type raikai machine composed of a mortar container made of earthenware and a pestle (rotation speed: 30 times / minute, 15 minutes), and a cylindrical small size of 33 mm in inner diameter × 15 mm in height. The pottery was filled with 20 g and dried in a far infrared drying oven at a temperature of 60 ° C. for 20 hours to solidify.
(Example 4-1) The surface of the unbaked shaped article, (Example 4-2) the surface of the unbaked shaped article coated with a glaze and dried, and (Example 4-3) the surface of the unbaked shaped article Glaze was applied and the surface baked at 1300 ° C. was painted.
After painting, each was fired at 1230 ° C. (Example 4-1), 1230 ° C. (Example 4-2), and 830 ° C. (Example 4-3). The coloring was vivid and beautiful.
[0061]
(Example 5)
Overcoat paint (90 parts of boric acid-lead-alumina-silica flux, 10 parts of inorganic pigment were added, mixed, pulverized and adjusted): 100 parts
Water-soluble polyurethane resin produced in Production Example 2: 50 parts
Water: 100 parts, 110 parts, 120 parts, and 130 parts were added to the paint for overglaze and the water-soluble polyurethane resin, respectively.
Samples of the above four types of preparations were prepared, and multiple painting was performed by brush painting. The painted product was dried at 820 ° C. after drying for 24 hours.
As a result, no paint fly or paint peeling was observed, and the surface was baked with good surface properties.
[0062]
It can be seen that the paint according to the present invention can be suitably used also for overpaints.
[0063]
(Example 6)
Inorganic pigment: 10% by weight
Glaze A (Noritake Campany-acid-resistant 37800 series flash for acid paint): 90% by weight
Was mixed with 30 parts by weight of the water-soluble polyurethane resin (as a solid content) produced in Production Example 3 with 100 parts by weight of the colored base material having the above composition to prepare the ceramic paint of the present invention. A glaze was applied to the unglazed product with the paint prepared according to the present invention, and the dried surface was painted. Baking was performed at 820 ° C to 850 ° C. The pigment was homogeneously melted and a desired color could be obtained.
[0064]
(Example 7)
70% by weight of inorganic pigment
Glaze B: 30% by weight
Was mixed with 30 parts by weight of the water-soluble polyester resin (as a solid content) produced in Production Example 1 to 100 parts by weight of the colored base material having the above composition to prepare the ceramic paint of the present invention. Glaze B was prepared by mixing at the following ratio.
Hiratsu feldspar 50% by weight Limestone 10% by weight
Kaolin 10% by weight Silica 30% by weight
A glaze was applied to the unglazed product, and the dried surface was painted with the paint according to the present invention prepared as described above. It baked at 1250 ° C-1300 ° C.
The pigment was homogeneously melted and a desired color could be obtained.
[0065]
(Example 8)
(Color test)
One color of pink (Al-Mn), two colors of red (Se-Cd-Zr), one color of yellow (V-Sn), two colors of zeal, including one color of Zr-Si Color (Sn-Zr-Si-V system), Grin-based one color (Co-Cr-Al-Zn-based), Blue-based four colors (Co-Zn-Al-based, Zr-Si-V-based), Brown-based 2 Color (Zn-Al-Fe-Cr system), one black system (Fe-Co-Cr system), three purple systems (Al-Mn-Co system), one gray system (Zr-Si-Co-Ni) A total of 20 colors were used as coloring substrates, and the ceramic paint of the present invention was manufactured in the same manner as in Examples 6 and 7, and a lime zinc-based ivory glaze was applied and dried on the surface. Coloring was performed and firing was performed for a color test.
The firing was performed at 1230 ° C. by oxidizing firing and reducing firing. Stable color development was obtained by any of the firing methods.
[0066]
(Example 9)
(Test of generated gas and residue)
After painting with the ceramic paint of the present invention, it was baked at 850 ° C. for 4 hours and examined for the presence of decomposition gas. No hydrocyanic acid gas was detected, and no generation of carbon monoxide was observed.
[0067]
Embodiment 10
(Base color)
The surface of the fired element was colored with Pigment 1 (V-Sn-based yellow), Pigment 2 (Fe-Co-Cr-based black), and Pigment 3 (Al-Mn-based pink). Reduction firing was performed at 1230 ° C. in an electric furnace.
As a result, in spite of the porous surface, the pigment was not absorbed by the surface, the brush was smoothly painted without taking a brush, and the coloring could be freely performed. In addition, the coloring of the paint was good without the base color affecting the coloring. As a result, a variety of expression methods became possible, and the style of the creator was utilized, and the effect of increasing the aesthetic value was obtained.
[0068]
【The invention's effect】
The ceramic paint according to the present invention has the following effects.
(1) Before brush-coating or stamp printing on the surface of the fired shaped product or on the glaze after glazing and drying, and after firing the glaze, before the glaze surface such as adding glue material Can be painted freely without the need for processing.
(2) Since painting is performed on the glaze during painting, free coloring work is possible by adjusting the color mixture with the base glaze without being restricted to the glaze color of the base.
(3) The same color can be reproduced beautifully without being affected by the transparency and color of the base glaze.
(4) Since it is possible to describe a thin film of 30 μm on the glaze, color shading and blurring are possible.
(5) A new painting method of applying the paint of the present invention to the unglazed material is presented.
(6) The overcoating effect can be achieved by omitting the processing step, especially the heating step only once in the main firing, and the cost and time required for the manufacturing step can be significantly reduced.
(7) It is possible to cope with the manufacture of small lots of paints, and various mixing ratios can be selected according to the intended use. It can be usefully used in a porcelain production site mainly for color expression including touch of a brush.
(8) It is possible to manufacture solid ceramic paints and liquid paints having various viscosities in relation to the layer thickness of the paint. There is no complication in using it by blending it, and it is possible to increase the added value of crafts by simple handling of simply dissolving it in the desired shade of water, and it is possible to develop a new expression method.
(9) In the case of a solid state, it is possible to maintain a uniform blending ratio of the binder and the pigment to the end, and to maintain the quality for a long period of time.
(10) In the pottery manufacturing process, which does not use a glaze, such as Bizen pottery, but uses the burning color and texture of the material, the appearance of fire color and firewood patterns, and the delicate and delicate use of the ceramic paint according to the present invention. By adding an unusual expression, a new creative expression can be expected.
(11) A stable color development can be obtained regardless of the calcination temperature in both oxidative calcination and reduction calcination.
(12) There is no odor during use and baking, and there is very little possibility of affecting environmental hormones.
Claims (9)
該素焼成形品表面に、請求項１乃至請求項７のいずれかに記載の陶磁器用絵具を用いて絵付けを行う工程、
焼成する工程で構成される、陶磁器の製造方法。A step of preparing an unfired shaped product,
A step of painting the surface of the fired shaped article using the ceramic paint according to any one of claims 1 to 7,
A method for producing ceramics, comprising a firing step.
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| JP2003142903A JP4420179B2 (en) | 2003-05-21 | 2003-05-21 | Ceramic paint |
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| JP2003142903A JP4420179B2 (en) | 2003-05-21 | 2003-05-21 | Ceramic paint |
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| JP4420179B2 JP4420179B2 (en) | 2010-02-24 |
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| JP2003142903A Expired - Fee Related JP4420179B2 (en) | 2003-05-21 | 2003-05-21 | Ceramic paint |
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| JP2011020878A (en) * | 2009-07-14 | 2011-02-03 | Tosoh Corp | Blue zirconia sintered compact |
| CN103144184A (en) * | 2013-03-22 | 2013-06-12 | 唐山红玫瑰陶瓷制品有限公司陶瓷研究院 | Ceramic glaze painting method |
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| JP2011020879A (en) * | 2009-07-14 | 2011-02-03 | Tosoh Corp | Gray zirconia sintered compact and method for manufacturing the same |
| JP2011020878A (en) * | 2009-07-14 | 2011-02-03 | Tosoh Corp | Blue zirconia sintered compact |
| JP2013151401A (en) * | 2011-12-27 | 2013-08-08 | Ikebukuro Horo Kogyo Kk | Glass lining composition |
| CN103144184A (en) * | 2013-03-22 | 2013-06-12 | 唐山红玫瑰陶瓷制品有限公司陶瓷研究院 | Ceramic glaze painting method |
| CN103144184B (en) * | 2013-03-22 | 2015-06-17 | 唐山红玫瑰陶瓷制品有限公司陶瓷研究院 | Ceramic glaze painting method |
| CN104649718A (en) * | 2015-01-23 | 2015-05-27 | 李宏亮 | Ceramic as well as daily necessities and artware prepared by same |
| JP2019508527A (en) * | 2016-01-12 | 2019-03-28 | 張利 | Painting pigment composition of BZ glaze and coating method |
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| CN115260832A (en) * | 2022-07-26 | 2022-11-01 | 李金朱 | Water-soluble ink block for ceramic painting and calligraphy |
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