JP3571540B2 - Filtration mold and method for producing ceramic sintered body using the mold - Google Patents
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Description
【０００１】
【発明の属する技術分野】
本発明は、セラミックス成形体の成形に用いられる濾過式成形型、スパッタリング法で使用される高純度スパッタリングターゲットおよびスパッタリングターゲットとして使用するのに好適な使用効率の高い肉厚差を有するセラミックス焼結体の製造方法に関する。
【０００２】
【従来の技術】
セラミックスの成形方法の一つである泥漿鋳込み成形は、石膏などの吸水性のある多孔質の密閉型にスラリーを加圧で注入し、型の全面あるいは２面から吸水する方法（特公平６−６５９号公報）が一般的である。しかし、成形型の全面あるいは２面から吸水した場合、成形体の中心部が最後に着肉するので、密度ムラや組成ムラなどの欠陥が発生しやすい。
【０００３】
また、泥漿鋳込み成形で使用される石膏は、水溶性であるため成形体中へのカルシウムの混入は防ぐことが出来ない。スパッタリングゲートようセラミックス焼結体は、高純度であることが望ましくいが、これにカルシウムが混入するとスパッタリングによって成膜した薄膜の導電性、透明性、エッチング性に悪影響を及ぼすことになる。
【０００４】
さらに、金型を用いた乾式プレス成形法においては、肉厚差のある成形体では成形密度が均一になりにくく、成形体に反りやクラックが発生しやすくなる。また成形サイズの大型化に伴ない金型やプレス設備が高価になるなどの特徴がある。
【発明が解決しようとする課題】
【０００５】
本発明の目的は、セラミックス焼結体の製造において不純物の混入が少なく、内部欠陥がなく密度ムラや組成ムラのない成形体や、肉厚差のある成形体を得るための安価な濾過式成形型およびその成形型を用いたセラミックス焼結体の製造法を提供することにある。
【０００６】
また、本発明の他の目的は、酸化インジウムと酸化錫を含むスラリーを上記の濾過式成形型を用いて成形し、得られた成形体を焼結して、高純度ＩＴＯ焼結体やスパッタリングゲートとして使用効率の高い肉厚差を有するＩＴＯ焼結体を製造する方法を提供することにある。
【０００７】
【課題を解決するための手段】
本発明者等は、泥漿鋳込み用石膏型に替わる成形型として、非水溶性の材料からなる濾過式成形型を用いて一方向の着肉を起こさせることにより、密度ムラや組成ムラがなく不純物の混入がない、高純度セラミックス焼結体が得られることを見い出した。また、同時に、前記の成形型の構造では、成形用下型にかかる負荷が小さいので、その材料として比較的強度の小さいものを使用できるため、成形サイズの大型化に対しても安価に成形型を提供できることを見い出した。さらに、成形用下型を凹凸形状に加工することにより肉厚差のある成形体が得られることを見い出した。
【０００８】
本発明は、下記の事項をその特徴としている。
（１） セラミックス原料スラリーから水分を減圧排水して成形体を得るための非水溶性材料からなる濾過式成形型であって、１個以上の水抜き孔を有する成形用下型と、この成形用下型の上に載置した通水性を有するフィルターと、このフィルターをシールするためのシール材を介して上面側から挟持する成形用型枠からなり、前記成形用下型、成形用型枠、シール材、およびフィルターが各々分解できるように組立てられており、該フィルター面側からのみスラリー中の水分を減圧排水することを特徴とする濾過式成形型。
（２） 成形用下型のフィルター面側が、凹凸形状を有することを特徴とする前記（１）に記載の濾過式成形型。
（３） セラミックス原料粉、イオン交換水と有機添加剤からなるスラリーを調製し、このスラリーを請求項（１）に記載の濾過式成形型に注入し、該フィルター面側からのみスラリー中の水分を減圧排水して成形体を製作し、得られたセラミックス成形体を乾燥脱脂後、焼成することを特徴とする高純度セラミックス焼結体の製造方法。
（４） セラミックス原料粉、イオン交換水と有機添加剤からなるスラリーを調製し、このスラリーを請求項（２）に記載の濾過式成形型に注入し、該フィルター面側からのみスラリー中の水分を減圧排水して成形体を製作し、得られたセラミックス成形体を乾燥脱脂後、焼成することを特徴とする肉厚差を有するセラミックス焼結体の製造方法。
（５） 酸化インジウム粉、酸化錫粉、イオン交換水および有機添加剤からなるスラリーを前記（１）に記載の濾過式成形型に注入し、フィルター面側からのみスラリー中の水分を減圧排水して成形体を製作し、得られたＩＴＯ成形体を乾燥脱脂後、焼成することを特徴とする高純度ＩＴＯ焼結体の製造方法。
（６） 酸化インジウム粉、酸化錫粉、イオン交換水および有機添加剤からなるスラリーを調製し、このスラリーを前記（２）に記載の濾過式成形型に注入し、フィルター面側からのみスラリー中の水分を減圧排水して成形体を製作し、得られたＩＴＯ成形体を乾燥脱脂後、焼成することを特徴とする肉厚差を有するＩＴＯ焼結体の製造方法。
【０００９】
【発明の実施の形態】
本発明の濾過式成形型は、図１に示すように、セラミックス原料スラリー１を成形用型枠２内に上部より注入し、下部に配置されている１個以上の水抜き孔６より減圧排水を行い成形体を得るものである。
【００１０】
濾過式成形型は、水抜き孔６をもつアルミ製あるいは樹脂（ポリプロピレン、ナイロン等）製の成形用下型３に、スラリー１中のセラミックス粉が透過しない通水性を有するフィルター４（例えば、ゴアテックス湿式フィルタークロス、ジャパンゴアテックス株式会社製）を載置した該成形用下型３と、シール材５を介してアルミ製の成形用型枠２を重ねた構造からなっている。
【００１１】
本発明の成形型では減圧排水時にかかる圧力は、フィルターと成形用下型間のみにかかるので比較的強度の低い材料を成形用下型として使用できる。
【００１２】
次に、本発明のセラミックスおよびＩＴＯ焼結体の製造方法について説明する。セラミックス焼結体の製造工程は図３に、ＩＴＯ焼結体の製造工程は図４に示す通りである。
【００１３】
（ａ）原料粉の調整
セラミックス原料粉を仮焼処理や粉砕処理を行うことで、１次粒子径や比表面積を調整することにより、スラリー化を容易にすることができる。
ＩＴＯ焼結体の場合では、酸化インジウム粉と酸化錫粉は市販品を使用できる。ただし市販の酸化インジウム粉を予め仮焼などの処理により粒成長させておくことが好ましい。酸化インジウム粉の１次粒子径が不適当になると成形密度の低下や密度ムラによる脱脂、焼結でのクラックや割れ、反りが大きくなるので、０．１〜０．５μｍの範囲とするのが好ましい。
【００１４】
（ｂ）スラリーの調製
セラミックス原料粉を単独または数種類をイオン交換水と有機添加剤（分散剤、バインダー、消泡剤）を加えてボールミル混合し、スラリーの調整を行う。ＩＴＯ焼結体の場合は、原料の酸化インジウム粉と酸化錫粉を予め乾式ボールミルで混合、粉砕する。酸化錫の組成は５〜１０重量％が好ましい。この際、イオン交換水１〜５重量％を加えておくと原料粉のポット壁への付着を減少させ、混合を十分に行なえる効果が期待できる。ボールミルのポットとしては、樹脂製ポットを使用するのが好ましい。またボールの材質は、比重が大きくて耐摩耗性に優れたジルコニアが好ましい。乾式ボールミルは、凝集粒子を解砕するとともに、粉の嵩密度を上げる効果がある。
【００１５】
次に、前記ボールミルポット中へイオン交換水を１０〜２５重量％、および有機添加剤（分散剤）を添加し、樹脂製ポットにて混合を行って原料粉を分散させる。分散剤としてはポリカルボン酸系分散剤が使用でき、添加量は０．２〜１．０重量％が好ましい。
【００１６】
さらに、有機添加剤（バインダー）を添加して混合を行いスラリーを得る。バインダーとしてはワックス系バインダーが使用でき、添加量は０．３〜１．０重量％が好ましい。スラリー粘度としては１００ｃｐ以下のスラリーを調製することが好ましい。スラリー粘度が高いと脱気が困難になったり、容器やボールへの付着によってスラリー回収率が低下する。
最後に、スラリーに有機添加剤（消泡剤）を添加して減圧脱気する。消泡剤としては、アミド系消泡剤が使用でき、添加量は０．０１〜０．５重量％が好ましい。
【００１７】
（ｃ）濾過式成形型による成形体の製作
脱気した前記スラリーを成形型に注入し、フィルターの下型面側を減圧し、スラリー中の水分をフィルター面側から減圧排水することにより成形する。減圧は−７００ｍｍＨｇより大きい方が好ましい。減圧には真空ポンプなどを使用することができる。
減圧排水時間は、成形体の着肉終了から約３０分後までがよい。減圧排水時間が短いと、成形体の成形用型枠からの離型性が悪くなりクラックが発生することがある。また減圧排水時間が長すぎると、減圧排水中に成形用型枠から成形体が離型して隙間から空気が吸引され、成形体の離型部分のみが急速に乾燥しクラックが発生することがある。
【００１８】
（ｄ）成形体の乾燥、脱脂
前記により得られた成形体を自然乾燥するのが好ましい。成形体は離型時に１０重量％程度の水分を含んでおり、成形体の乾燥を乾燥器などを使用して急速に行うと、乾燥ムラから成形体の反り、クラックが発生することがある。
さらに、乾燥した成形体の脱脂を行う。成形体の脱脂を行わないと焼成時に成形体に反りやクラック、割れが発生しやすくなる。脱脂は熱風循環式脱脂炉等を使用して４００〜６００℃で加熱し、残留水分およびバインダーを除去することが好ましい。
【００１９】
（ｅ）成形体の焼成
成形体を焼成することにより高純度セラミックス焼結体を得る。ＩＴＯ焼結体の場合は焼成温度は１４００〜１６００℃が好ましい。焼成雰囲気は大気および酸素が使用できるが、酸素雰囲気を用いることが高密度の焼結体を得るためには好ましい。
【００２０】
本発明の成形型について従来型と比較した利点を、表１に示す。本発明の成形型は従来の石膏型、プレス金型に比べ、密度ムラや組成ムラがなく、不純物混入もなく、また大型化するための費用も少なくてすむ等の利点を有している。また、肉厚差を有する成形体を成形するに際しても同様の利点がある。
【００２１】
【表１】
【実施例】
以下に、本発明を実施例と比較例によりさらに説明する。
実施例１
市販のローソーダアルミナ粉１５０００ｇ、イオン交換水３４５０ｇ、ポリカルボン酸系分散剤１５０ｇ、ワックス系バインダー１５０ｇと鉄芯入り樹脂ボールを樹脂製ポットに入れ４０時間ボールミル混合を行った。このスラリーの濃度は８３％で、平均粒子径は０．７６μｍ、粘度は１０５ｃｐだった。
【００２３】
スラリーを減圧脱気後、成形サイズ１０５０ｍｍ×１１００ｍｍの成形よう型枠がアルミニウム製で成形用下型が樹脂製の本発明成形型に注入し、フィルター面側より減圧排水し成形体を得た。
フィルターは、ゴアテックス湿式フィルタークロス、ジャパンゴアテックス株式会社製を用いた。このフィルターは織布またはフェルト上に多孔性の樹脂膜を片面側のみ付着させた構造で形成されており、樹脂の裏面側は織布またはフェルトからなり、通水空間を有し、多孔性の樹脂膜と下型との間には水が自由に移動できる通路が形成されている。
【００２４】
成形体を自然乾燥後、脱脂処理を４５０℃で行なった。脱脂後の成形体には密度ムラによる反りやクラックは発生せず、寸法は１０４９ｍｍ×１０９９ｍｍ×１０．２ｍｍで、密度は５５％（２．１９ｇ／ｃｍ３ ）だった。
スラリー濃度の定義は次の通りである。
スラリー濃度（％）＝溶質重量／（溶質重量＋溶媒重量）×１００
【００２５】
実施例２
市販の酸化錫粉２５０ｇ、イオン交換水１．２５ｇとジルコニアボールを樹脂製ポットに入れ２０時間ボールミル混合を行った。次にイオン交換水２３３ｇとポリカルボン酸系分散剤２ｇを入れ１時間ボールミル混合した。１時間後にワックス系バインダーを２．５ｇ添加し、１９時間ボールミル混合を行った。このスラリーの濃度は８３％、平均粒径は１．１μｍ、粘度は７１ｃｐだった。
【００２６】
スラリーを減圧脱気後、成形サイズ７６ｍｍφであること以外は実施例１と同様の材質、構造の成形型に注入し、減圧−７６０ｍｍＨｇで減圧排水し成形体を得た。成形体を自然乾燥後、脱脂処理を６００℃で３時間行った。その後、酸素雰囲気にて１５００℃で８時間焼成し酸化錫焼結体を得た。焼結体に密度ムラによる反りやクラックは発生せず、密度は６６．５％（４．６ｇ／ｃｍ３ ）であった。また不純物としてカルシュウムが混入しない高純度の焼結体が得られた。
【００２７】
実施例３
酸化インジウム粉７２００ｇ、酸化錫粉８００ｇとイオン交換水２４０ｇおよび直径５ｍｍのジルコニアボールを樹脂製ポットに入れ、２０時間ボールミル混合を行った。次に、イオン交換水１４４０ｇとポリカルボン酸系分散剤５６ｇを入れ１時間ボールミル混合した。１時間後にワックス系バインダーを８０ｇ添加し１９時間ボールミル混合を行った。
【００２８】
次に、スラリーにアミド系消泡剤１．６ｇを添加し減圧脱気を行った。このスラリーの濃度は８３％で、平均粒径は０．５μｍ、粘度は３３ｃｐだった。このスラリーを成形サイズ３００ｍｍ×７００ｍｍで成形用下型がアルミニウム製であること以外は実施例１と同様の構造成形型に注入し、減圧−７６０ｍｍＨｇで減圧排水し、成形体を得た。
【００２９】
成形体を自然乾燥、脱脂処理を６００℃で３時間行った。その後、酸素雰囲気にて１５５０℃で８時間焼成した。ＩＴＯ焼結体には密度ムラによる反りやクラックは発生しなかった。また、酸化錫の偏析がなく、カルシウムの混入しない高純度ＩＴＯ焼結体を得た。ＩＴＯ焼結体の寸法は、２４７ｍｍ×５７８ｍｍ×７．３ｍｍであり、密度は９８．１％（７．０１ｇ／ｃｍ３ ）であった。
【００３０】
実施例４
酸化インジウム粉１８０００ｇ、酸化錫粉２０００ｇとイオン交換水６００ｇおよび直径５ｍｍのジルコニアボールを樹脂製ポットに入れ２０時間ボールミル混合を行った。次に、イオン交換水３５９２ｇとポリカルボン酸系分散剤１６０ｇを入れ、１時間ボールミル混合した。１時間後にワックス系バインダーを２００ｇ添加し、１９時間ボールミル混合を行った。
【００３１】
スラリーにアミド系消泡剤４ｇを添加し減圧脱気を行った。このスラリーの濃度は８３％で、平均粒径は０．５μｍ、粘度は４０ｃｐだった。このスラリーを成形サイズ３７５ｍｍ×１２７０ｍｍ成形用下型がアルミニウム製であること以外は実施例１と同様の構造成形型に注入し、減圧−７６０ｍｍＨｇで減圧排水し成形体を得た。
【００３２】
成形体を自然乾燥、脱脂処理を６００℃で３時間行った。その後、酸素雰囲気にて１５５０℃で８時間焼成した。ＩＴＯ焼結体には密度ムラによる反りやクラックは発生しなかった。また、酸化錫の偏析がなく、カルシウムの混入しない高純度ＩＴＯ焼結体を得た。ＩＴＯ焼結体の寸法は、３０８ｍｍ×１０４６ｍｍ×７．９ｍｍであり、密度は９８．８％（７．０６ｇ／ｃｍ３ ）であった。
【００３３】
実施例５
酸化インジウム粉９００ｇ、酸化錫粉１００ｇとイオン交換水３０ｇおよび直径５ｍｍのジルコニアボールを樹脂製ポットに入れ、２０時間ボールミル混合を行った。次に、イオン交換水１７８ｇとポリカルボン酸系分散剤７．９ｇを入れ、１時間ボールミル混合した。１時間後にワックス系バインダーを９．９ｇ添加し、１９時間ボールミル混合を行った。
【００３４】
スラリーにアミド系消泡剤０．２ｇを添加し減圧脱気を行った。このスラリーの濃度は８３％で、平均粒径は０．４６μｍ、粘度は１５ｃｐだった。このスラリーを成形サイズ１９０ｍｍφで成形用下型がアルミニウム製であること以外は実施例１と同様の構造成形型に注入し、減圧−７６０ｍｍＨｇで減圧排水し成形体を得た。
【００３５】
成形体を自然乾燥、脱脂処理を６００℃で３時間行った。その後、酸素雰囲気にて１５５０℃で８時間焼成した。ＩＴＯ焼結体には密度ムラによる反りやクラックは発生しなかった。また、酸化錫の偏析がなく、カルシウムの混入しない高純度ＩＴＯ焼結体を得た。ＩＴＯ焼結体の寸法は１５７ｍｍ×７．９ｍｍであり、密度は９９．５％（７．１１ｇ／ｃｍ３ ）であった。
【００３６】
実施例６
酸化インジウム粉７２０ｇ、酸化錫粉８０ｇとイオン交換水２４ｇおよび直径１０ｍｍのジルコニアボールを樹脂製ポットに入れ、２０時間ボールミル混合を行った。次に、イオン交換水１２８ｇとポリカルボン酸系分散剤６．４ｇを入れ、１時間ボールミル混合した。１時間後にワックス系バインダーを８．０ｇ添加し、１９時間ボールミル混合を行った。
【００３７】
スラリーにアミド系消泡剤０．４ｇを添加し減圧脱気を行った。このスラリーの濃度は８３％で、平均粒径は０．５３μｍ、粘度は２８ｃｐだった。このスラリーを成形サイズ１９０ｍｍφでフィルター面側に同心円状の深さ５ｍｍ幅３０ｍｍの凹部加工であること以外は実施例１と同様の構造の成形型に注入し、減圧−７１０ｍｍＨｇで減圧排水し成形体を得た。
【００３８】
成形体を自然乾燥、脱脂処理を６００℃で３時間行った。その後、酸素雰囲気にて１５５０℃で８時間焼成した。ＩＴＯ焼結体には密度ムラによる反りやクラックは発生しなかった。ＩＴＯ焼結体の寸法は１５６．６ｍｍφ×３．５２（薄肉部）「６．５６ｍｍ（厚肉部）」であり、密度は９９．３％（７．１０ｇ／ｃｍ３ ）だった。
【００３９】
比較例１
酸化インジウム粉６９３０ｇ、酸化錫粉７７０ｇとジルコニアボールを樹脂製ポットに入れ２０時間ボールミル混合を行った。ポットから取り出した原料粉に濃度４重量％のポリビニルアルコール水溶液を６．０重量％添加して撹拌混合した。次に、この原料粉を圧力５００ｋｇｆ／ｃｍ２ でプレス後粉砕して６０メッシュ以下に整粒した。この整粒粉を成形サイズ２００×９８０の金型に入れ圧力１０００ｋｇｆ／ｃｍ２ で成形した。
【００４０】
成形体には密度ムラによると思われるクラックが発生した。成形体の寸法は２０１．０ｍｍ×９８２．０×９．２６ｍｍであり、密度は６１．０％（４．３６ｇ／ｃｍ３ ）だった。
【００４１】
比較例２
実施例５のスラリーを成形サイズ１９０ｍｍφ×８．５ｍｍの石膏型に圧力１．０ｋｇ／ｃｍ２ で鋳込み、成形体を得た。成形体を自然乾燥後、６００℃で３時間脱脂した。
【００４２】
その後、酸素雰囲気にて１５５０℃で８時間焼成しＩＴＯ焼結体を得た。このときＩＴＯ焼結体の密度は９７．２％（６．９５ｇ／ｃｍ３ ）だった。ＩＴＯ焼結体内部の中央部分にはスジ状の欠陥が見られＥＰＭＡ分析により酸化錫の偏析が観察された。また、不純物としてカルシウムが３５ｐｐｍ検出された。
【００４３】
【発明の効果】
本発明の成形型を用いることにより、スラリー中の水分を片側からのみ減圧排水する濾過方式で成形体を製作するため着肉が一方向にのみ起こり、成形体内部に密度ムラや組成ムラなど欠陥が発生しない。また鋳込み用型材料からの不純物混入がなく高純度の成形体が得られる。さらに、本発明の成形型を用いることにより、肉厚差のある成形体を得ることができる。
【００４４】
また従来法のプレス成形や加圧鋳込みでは成形サイズの大型化に伴い成形型材やプレス機などの設備強度を上げる必要があり設備費が高価になるが、本発明の成形型では減圧排水時にかかる圧力はフィルターと成形用下型間のみにかかるので、比較的強度の低い材料を成形用下型として使用でき、成形サイズが大型化しても材料費は安価にできる。
【図面の簡単な説明】
【図１】本発明に係る濾過式成形型（平板成形型）の構造を示す説明図である。
【図２】本発明に係る濾過式成形型（凹凸形状成形型）の構造を示す説明図である。
【図３】本発明に係る濾過式成形法によるセラミックス焼結体の製造工程を示す説明図である。
【図４】本発明に係る濾過式成形法によるＩＴＯ焼結体の製造工程を示す説明図である。
【符号の説明】
１ スラリー
２ 成形用型枠
３ 成形用下型
４ フィルター
５ シール材
６ 水抜き孔[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a filtration mold used for molding a ceramic molded body, a high-purity sputtering target used in a sputtering method, and a ceramic sintered body having a thickness difference with high use efficiency suitable for use as a sputtering target. And a method for producing the same.
[0002]
[Prior art]
Slurry cast molding, which is one of the ceramic molding methods, is a method in which a slurry is injected under pressure into a water-absorbing porous closed mold such as gypsum, and water is absorbed from the entire surface or two surfaces of the mold (Japanese Patent Publication No. No. 659) is common. However, when water is absorbed from the entire surface or two surfaces of the molding die, defects such as density unevenness and composition unevenness are likely to occur because the central portion of the molded body is finally deposited.
[0003]
Further, since gypsum used in the slip casting is water-soluble, it is not possible to prevent calcium from being mixed into the molded body. It is desirable that the ceramic sintered body such as a sputtering gate has high purity. However, if calcium is mixed into the ceramic sintered body, it adversely affects the conductivity, transparency, and etching properties of a thin film formed by sputtering.
[0004]
Further, in a dry press molding method using a mold, a molded article having a difference in wall thickness is difficult to have a uniform molding density, and the molded article is likely to be warped or cracked. In addition, there is a feature that the mold and the press equipment become expensive as the molding size increases.
[Problems to be solved by the invention]
[0005]
An object of the present invention is to provide an inexpensive filtration molding method for obtaining a molded body having less internal impurities and having no density unevenness or composition unevenness, or a molded body having a difference in wall thickness, in the production of a ceramic sintered body. An object of the present invention is to provide a mold and a method for producing a ceramic sintered body using the mold.
[0006]
Another object of the present invention is to form a slurry containing indium oxide and tin oxide using the above-mentioned filtration mold, sinter the obtained compact, and form a high-purity ITO sintered compact or An object of the present invention is to provide a method of manufacturing an ITO sintered body having a thickness difference with high use efficiency as a gate.
[0007]
[Means for Solving the Problems]
The present inventors use a filtration mold made of a water-insoluble material as a mold instead of a gypsum mold for slip casting to cause one-way inking, so that there is no density unevenness or composition unevenness and impurities It has been found that a high-purity ceramics sintered body free from contamination can be obtained. At the same time, in the structure of the molding die described above, the load on the lower molding die is small, so that a material having a relatively low strength can be used as the material, so that the molding die can be manufactured at a low cost even if the molding size is increased. Can be provided. Furthermore, it has been found that a molded body having a difference in wall thickness can be obtained by processing the lower mold for molding into an uneven shape.
[0008]
The present invention has the following features.
(1) A filtration mold made of a water-insoluble material for obtaining a compact by draining water from a ceramic raw material slurry under reduced pressure, comprising a lower mold having at least one drain hole, A filter having water permeability placed on the lower mold, and a molding mold sandwiched from the upper side via a sealing material for sealing the filter, wherein the lower mold for molding, the molding mold , A sealing material, and a filter are assembled so that they can be disassembled, and water in the slurry is drained under reduced pressure only from the filter surface side.
(2) The filtration molding die according to the above (1), wherein the filter surface side of the molding lower die has an uneven shape.
(3) A slurry composed of ceramic raw material powder, ion-exchanged water and an organic additive is prepared, and the slurry is poured into the filtration mold according to claim (1), and the water content in the slurry is only from the filter surface side. A high-purity ceramic sintered body, characterized in that a molded body is produced by draining water under reduced pressure, and the obtained ceramic molded body is dried, degreased, and fired.
(4) A slurry comprising a ceramic raw material powder, ion-exchanged water and an organic additive is prepared, and the slurry is poured into the filtration mold according to claim (2), and the water content in the slurry is only from the filter surface side. A method for producing a ceramic sintered body having a thickness difference, characterized by producing a molded body by draining water under reduced pressure, drying and degreasing the obtained ceramic molded body, and then firing.
(5) A slurry composed of indium oxide powder, tin oxide powder, ion-exchanged water and an organic additive is poured into the filtration mold described in (1) above, and the water in the slurry is drained under reduced pressure only from the filter surface side. A method for producing a high-purity ITO sintered body, characterized in that a molded body is manufactured by drying, the obtained ITO molded body is dried and degreased, and then fired.
(6) A slurry composed of indium oxide powder, tin oxide powder, ion-exchanged water and an organic additive is prepared, and this slurry is poured into the filtration mold described in the above (2), and the slurry is contained only from the filter surface side. A method for producing an ITO sintered body having a difference in thickness, characterized in that a molded body is manufactured by draining the water under reduced pressure, and the obtained ITO molded body is dried, degreased, and fired.
[0009]
BEST MODE FOR CARRYING OUT THE INVENTION
As shown in FIG. 1, the filtration mold of the present invention injects a ceramic raw material slurry 1 into a
[0010]
The filtration type mold is provided with a filter 4 (for example, Gore-Tech) having water permeability through which ceramic powder in the slurry 1 does not pass through a
[0011]
In the molding die of the present invention, the pressure applied at the time of draining under reduced pressure is applied only between the filter and the lower molding die, so that a material having relatively low strength can be used as the lower molding die.
[0012]
Next, a method for producing the ceramic and the ITO sintered body of the present invention will be described. The manufacturing process of the ceramic sintered body is as shown in FIG. 3, and the manufacturing process of the ITO sintered body is as shown in FIG.
[0013]
(A) Adjustment of Raw Material Powder Sintering can be facilitated by adjusting the primary particle diameter and the specific surface area by performing calcination treatment or pulverization treatment on the ceramic raw material powder.
In the case of the ITO sintered body, commercially available indium oxide powder and tin oxide powder can be used. However, it is preferable that a commercially available indium oxide powder is previously grown by a treatment such as calcination. If the primary particle size of the indium oxide powder is inappropriate, the molding density decreases, degreasing due to density unevenness, cracks, cracks, and warpage during sintering increase, so that the range is 0.1 to 0.5 μm. preferable.
[0014]
(B) Preparation of Slurry A single or several types of ceramic raw material powder are added to ion-exchanged water and an organic additive (dispersant, binder, defoaming agent) and mixed in a ball mill to prepare a slurry. In the case of an ITO sintered body, raw materials of indium oxide powder and tin oxide powder are mixed and pulverized in advance by a dry ball mill. The composition of tin oxide is preferably 5 to 10% by weight. At this time, if 1 to 5% by weight of ion-exchanged water is added, the effect of reducing the adhesion of the raw material powder to the pot wall and sufficiently mixing can be expected. It is preferable to use a resin pot as the ball mill pot. The material of the ball is preferably zirconia having a large specific gravity and excellent wear resistance. A dry ball mill has the effect of breaking up agglomerated particles and increasing the bulk density of the powder.
[0015]
Next, 10 to 25% by weight of ion-exchanged water and an organic additive (dispersant) are added to the ball mill pot, and the mixture is mixed in a resin pot to disperse the raw material powder. As the dispersant, a polycarboxylic acid-based dispersant can be used, and the addition amount is preferably 0.2 to 1.0% by weight.
[0016]
Further, an organic additive (binder) is added and mixed to obtain a slurry. As the binder, a wax-based binder can be used, and the addition amount is preferably 0.3 to 1.0% by weight. It is preferable to prepare a slurry having a slurry viscosity of 100 cp or less. If the slurry viscosity is high, deaeration becomes difficult, and the slurry recovery rate decreases due to adhesion to containers and balls.
Finally, an organic additive (antifoaming agent) is added to the slurry, and the slurry is degassed under reduced pressure. As the antifoaming agent, an amide-based antifoaming agent can be used, and the addition amount is preferably 0.01 to 0.5% by weight.
[0017]
(C) Production of a molded body by a filtration molding die The degassed slurry is poured into a molding die, the lower surface of the filter is depressurized, and the water in the slurry is depressurized and drained from the filter surface. . The reduced pressure is preferably larger than -700 mmHg. A vacuum pump or the like can be used for pressure reduction.
The decompression drainage time is preferably from about 30 minutes after the end of the molding. If the decompression drainage time is short, the releasability of the molded body from the molding frame is deteriorated, and cracks may occur. If the decompression drainage time is too long, the molded product is released from the molding frame during the decompression drainage, and air is sucked from the gap, and only the release part of the molded product is rapidly dried and cracks may occur. is there.
[0018]
(D) Drying and Degreasing of the Molded Article It is preferable to naturally dry the molded article obtained as described above. The molded body contains about 10% by weight of water at the time of release from the mold, and if the molded body is rapidly dried using a dryer or the like, the molded body may warp or crack due to uneven drying.
Further, the dried molded body is degreased. If the molded body is not degreased, the molded body is likely to be warped, cracked, or cracked during firing. Degreasing is preferably performed by heating at 400 to 600 ° C. using a hot air circulation type degreasing furnace or the like to remove residual moisture and binder.
[0019]
(E) Firing of the molded body A high-purity ceramic sintered body is obtained by firing the molded body. In the case of an ITO sintered body, the firing temperature is preferably 1400 to 1600 ° C. As the firing atmosphere, air and oxygen can be used, but it is preferable to use an oxygen atmosphere in order to obtain a high-density sintered body.
[0020]
Table 1 shows the advantages of the mold of the present invention as compared with the conventional mold. The molding die of the present invention has advantages such as non-uniform density and non-uniform composition, no contamination of impurities, and low cost for upsizing, as compared with the conventional gypsum die and press die. Further, there is a similar advantage when molding a molded body having a difference in wall thickness.
[0021]
[Table 1]
【Example】
Hereinafter, the present invention will be further described with reference to Examples and Comparative Examples.
Example 1
15000 g of commercially available low soda alumina powder, 3450 g of ion-exchanged water, 150 g of a polycarboxylic acid-based dispersant, 150 g of a wax-based binder, and a resin ball containing an iron core were placed in a resin pot and mixed with a ball mill for 40 hours. The concentration of this slurry was 83%, the average particle size was 0.76 μm, and the viscosity was 105 cp.
[0023]
After the slurry was degassed under reduced pressure, it was poured into a molding die of the present invention in which a molding frame having a molding size of 1050 mm × 1100 mm was formed of aluminum and the lower molding die was formed of resin, and drained under reduced pressure from the filter side to obtain a molded product.
The filter used was Gore-Tex wet filter cloth, manufactured by Japan Gore-Tex Corporation. This filter is formed with a structure in which a porous resin film is adhered on one side only on a woven fabric or felt, and the back surface of the resin is made of a woven fabric or felt, has a water passage space, A passage through which water can freely move is formed between the resin film and the lower mold.
[0024]
After the molded body was naturally dried, a degreasing treatment was performed at 450 ° C. The molded article after degreasing did not generate warpage or crack due to density unevenness, the dimensions were 1049 mm × 1099 mm × 10.2 mm, and the density was 55% (2.19 g / cm 3 ).
The definition of the slurry concentration is as follows.
Slurry concentration (%) = solute weight / (solute weight + solvent weight) × 100
[0025]
Example 2
250 g of commercially available tin oxide powder, 1.25 g of ion-exchanged water and zirconia balls were placed in a resin pot and mixed with a ball mill for 20 hours. Next, 233 g of ion-exchanged water and 2 g of a polycarboxylic acid-based dispersant were added and mixed in a ball mill for 1 hour. One hour later, 2.5 g of a wax-based binder was added, and ball mill mixing was performed for 19 hours. The concentration of this slurry was 83%, the average particle size was 1.1 μm, and the viscosity was 71 cp.
[0026]
After the slurry was degassed under reduced pressure, it was poured into a molding die having the same material and structure as in Example 1 except that the molding size was 76 mmφ, and the slurry was drained under reduced pressure at -760 mmHg to obtain a molded product. After the molded body was naturally dried, a degreasing treatment was performed at 600 ° C. for 3 hours. Then, it was baked at 1500 ° C. for 8 hours in an oxygen atmosphere to obtain a tin oxide sintered body. No warpage or cracks due to density unevenness occurred in the sintered body, and the density was 66.5% (4.6 g / cm 3 ). A high-purity sintered body in which calcium was not mixed as an impurity was obtained.
[0027]
Example 3
7,200 g of indium oxide powder, 800 g of tin oxide powder, 240 g of ion-exchanged water, and zirconia balls having a diameter of 5 mm were placed in a resin pot, and mixed in a ball mill for 20 hours. Next, 1440 g of ion-exchanged water and 56 g of a polycarboxylic acid-based dispersant were added and mixed in a ball mill for 1 hour. One hour later, 80 g of a wax-based binder was added, and ball mill mixing was performed for 19 hours.
[0028]
Next, 1.6 g of an amide-based antifoaming agent was added to the slurry, and deaeration was performed under reduced pressure. The concentration of this slurry was 83%, the average particle size was 0.5 μm, and the viscosity was 33 cp. This slurry was poured into a structural mold similar to that in Example 1 except that the mold was 300 mm × 700 mm and the lower mold was made of aluminum, and was drained under reduced pressure at −760 mmHg to obtain a molded article.
[0029]
The molded body was naturally dried and degreased at 600 ° C. for 3 hours. Then, it was baked at 1550 ° C. for 8 hours in an oxygen atmosphere. No warpage or crack due to density unevenness occurred in the ITO sintered body. In addition, a high-purity ITO sintered body free from segregation of tin oxide and containing no calcium was obtained. The dimensions of the ITO sintered body were 247 mm × 578 mm × 7.3 mm, and the density was 98.1% (7.01 g / cm 3 ).
[0030]
Example 4
18000 g of indium oxide powder, 2000 g of tin oxide powder, 600 g of ion-exchanged water, and zirconia balls having a diameter of 5 mm were placed in a resin pot and mixed with a ball mill for 20 hours. Next, 3592 g of ion-exchanged water and 160 g of a polycarboxylic acid-based dispersant were added and mixed for 1 hour with a ball mill. One hour later, 200 g of a wax-based binder was added, and ball mill mixing was performed for 19 hours.
[0031]
4 g of an amide-based antifoaming agent was added to the slurry, and deaeration was performed under reduced pressure. The concentration of this slurry was 83%, the average particle size was 0.5 μm, and the viscosity was 40 cp. This slurry was poured into a structural mold similar to that of Example 1 except that the lower mold for molding was 375 mm × 1270 mm made of aluminum, and drained under reduced pressure at −760 mmHg to obtain a molded article.
[0032]
The molded body was naturally dried and degreased at 600 ° C. for 3 hours. Then, it was baked at 1550 ° C. for 8 hours in an oxygen atmosphere. No warpage or crack due to density unevenness occurred in the ITO sintered body. In addition, a high-purity ITO sintered body free from segregation of tin oxide and containing no calcium was obtained. The dimensions of the ITO sintered body were 308 mm × 1046 mm × 7.9 mm, and the density was 98.8% (7.06 g / cm 3 ).
[0033]
Example 5
900 g of indium oxide powder, 100 g of tin oxide powder, 30 g of ion-exchanged water, and zirconia balls having a diameter of 5 mm were placed in a resin pot, and mixed in a ball mill for 20 hours. Next, 178 g of ion-exchanged water and 7.9 g of a polycarboxylic acid-based dispersant were added and mixed for 1 hour with a ball mill. One hour later, 9.9 g of a wax-based binder was added, and ball mill mixing was performed for 19 hours.
[0034]
0.2 g of an amide-based antifoaming agent was added to the slurry, and deaeration was performed under reduced pressure. The concentration of this slurry was 83%, the average particle size was 0.46 μm, and the viscosity was 15 cp. This slurry was poured into a structural mold in the same manner as in Example 1 except that the lower mold for molding was made of aluminum with a mold size of 190 mmφ, and was drained under reduced pressure at -760 mmHg to obtain a molded article.
[0035]
The molded body was naturally dried and degreased at 600 ° C. for 3 hours. Then, it was baked at 1550 ° C. for 8 hours in an oxygen atmosphere. No warpage or crack due to density unevenness occurred in the ITO sintered body. In addition, a high-purity ITO sintered body free from segregation of tin oxide and containing no calcium was obtained. The dimensions of the ITO sintered body were 157 mm × 7.9 mm, and the density was 99.5% (7.11 g / cm 3 ).
[0036]
Example 6
720 g of indium oxide powder, 80 g of tin oxide powder, 24 g of ion-exchanged water, and zirconia balls having a diameter of 10 mm were placed in a resin pot and mixed with a ball mill for 20 hours. Next, 128 g of ion-exchanged water and 6.4 g of a polycarboxylic acid-based dispersant were added, and mixed with a ball mill for 1 hour. One hour later, 8.0 g of a wax-based binder was added, and ball mill mixing was performed for 19 hours.
[0037]
0.4 g of an amide-based antifoaming agent was added to the slurry, and deaeration was performed under reduced pressure. The concentration of this slurry was 83%, the average particle size was 0.53 μm, and the viscosity was 28 cp. This slurry was poured into a mold having the same structure as in Example 1 except that a concavity of 5 mm in depth and 30 mm in width was concentrically formed on the filter surface side with a molding size of 190 mmφ, and drained under reduced pressure at -710 mmHg. Got.
[0038]
The molded body was naturally dried and degreased at 600 ° C. for 3 hours. Then, it was baked at 1550 ° C. for 8 hours in an oxygen atmosphere. No warpage or crack due to density unevenness occurred in the ITO sintered body. The dimensions of the ITO sintered body were 156.6 mmφ × 3.52 (thin part) and “6.56 mm (thick part)”, and the density was 99.3% (7.10 g / cm 3 ).
[0039]
Comparative Example 1
6930 g of indium oxide powder, 770 g of tin oxide powder and zirconia balls were placed in a resin pot and mixed with a ball mill for 20 hours. An aqueous solution of polyvinyl alcohol having a concentration of 4% by weight was added to the raw material powder taken out of the pot at a concentration of 6.0% by weight, followed by stirring and mixing. Next, this raw material powder was pressed at a pressure of 500 kgf / cm 2 and then pulverized and sized to 60 mesh or less. The sized powder was placed in a mold having a molding size of 200 × 980 and molded at a pressure of 1000 kgf / cm 2 .
[0040]
Cracks occurred in the molded article, which were considered to be due to uneven density. The dimensions of the molded body were 201.0 mm × 982.0 × 9.26 mm, and the density was 61.0% (4.36 g / cm 3 ).
[0041]
Comparative Example 2
The slurry of Example 5 was cast into a gypsum mold having a molding size of 190 mmφ × 8.5 mm at a pressure of 1.0 kg / cm 2 to obtain a molded body. After the molded body was naturally dried, it was degreased at 600 ° C. for 3 hours.
[0042]
Then, it was baked at 1550 ° C. for 8 hours in an oxygen atmosphere to obtain an ITO sintered body. At this time, the density of the ITO sintered body was 97.2% (6.95 g / cm 3 ). Streak-like defects were observed in the central portion inside the ITO sintered body, and segregation of tin oxide was observed by EPMA analysis. Also, 35 ppm of calcium was detected as an impurity.
[0043]
【The invention's effect】
By using the molding die of the present invention, in order to produce a molded body by a filtration method in which the water in the slurry is drained under reduced pressure only from one side, inking occurs only in one direction, and defects such as density unevenness and composition unevenness occur inside the molded body. Does not occur. In addition, a molded product of high purity can be obtained without impurities from the casting mold material. Further, by using the mold of the present invention, a molded body having a difference in wall thickness can be obtained.
[0044]
In addition, in conventional press molding and pressure casting, it is necessary to increase the strength of equipment such as a molding material and a press machine due to the increase in molding size, and equipment costs are expensive. Since pressure is applied only between the filter and the lower molding die, a material having relatively low strength can be used as the lower molding die, and the material cost can be reduced even if the molding size is increased.
[Brief description of the drawings]
FIG. 1 is an explanatory view showing the structure of a filtration mold (flat mold) according to the present invention.
FIG. 2 is an explanatory view showing a structure of a filtration mold (a mold having an uneven shape) according to the present invention.
FIG. 3 is an explanatory view showing a manufacturing process of a ceramic sintered body by a filtration molding method according to the present invention.
FIG. 4 is an explanatory view showing a production process of an ITO sintered body by a filtration molding method according to the present invention.
[Explanation of symbols]
DESCRIPTION OF SYMBOLS 1
Claims (6)
１個以上の水抜き孔を有する成形用下型と、
この成形用下型の上に載置した通水性を有する、織布またはフェルト上に多孔性の樹脂膜を片面側のみ付着させたフィルターと、
このフィルターをシールするためのシール材を介して上面側から挟持する成形用型枠からなり、
前記成形用下型、成形用型枠、シール材、およびフィルターが各々分解できるように組立てられており、該フィルター面側からのみスラリー中の水分を減圧排水することを特徴とする濾過式成形型。A filtration mold made of a water-insoluble material for obtaining a ceramic molded body for a sputtering target by draining water under reduced pressure from a ceramic raw material slurry,
And the lower mold for forming shapes that have a one or more drain holes,
A filter having a water-permeable material placed on the lower mold for molding , a porous resin film adhered to only one side on a woven fabric or felt ,
It consists of a molding frame that is clamped from the top side via a sealing material to seal this filter,
The lower mold for molding, the mold for molding, the sealing material, and the filter are assembled so that they can be disassembled, and the filtration mold is characterized in that the water in the slurry is drained under reduced pressure only from the filter surface side. .
このスラリーを請求項１に記載の濾過式成形型に注入し、
該フィルター面側からのみスラリー中の水分を減圧排水して成形体を製作し、
得られたセラミックス成形体を乾燥脱脂後、焼成すること
を特徴とする高純度セラミックス焼結体スパッタリングターゲットの製造方法。Prepare a slurry consisting of ceramic raw material powder, ion-exchanged water and organic additives,
Injecting the slurry into the filtration mold according to claim 1,
A compact is manufactured by draining the water in the slurry under reduced pressure only from the filter surface side,
A method for producing a sputtering target of a high-purity ceramic sintered body, comprising drying and degreasing the obtained ceramic molded body, followed by firing.
このスラリーを請求項２に記載の濾過式成形型に注入し、
該フィルター面側からのみスラリー中の水分を減圧排水して成形体を製作し、
得られたセラミックス成形体を乾燥脱脂後、焼成すること
を特徴とする肉厚差を有するセラミックス焼結体スパッタリングターゲットの製造方法。Prepare a slurry consisting of ceramic raw material powder, ion-exchanged water and organic additives,
Injecting the slurry into the filtration mold according to claim 2,
A compact is manufactured by draining the water in the slurry under reduced pressure only from the filter surface side,
A method for producing a ceramic sintered body sputtering target having a thickness difference, wherein the obtained ceramic molded body is dried, degreased, and fired.
このスラリーを請求項１に記載の濾過式成形型に注入し、
フィルター面側からのみスラリー中の水分を減圧排水して成形体を製作し、
得られたＩＴＯ成形体を乾燥脱脂後、焼成すること
を特徴とする高純度ＩＴＯ焼結体スパッタリングターゲットの製造方法。Prepare a slurry composed of indium oxide powder, tin oxide powder, ion-exchanged water and organic additives,
Injecting the slurry into the filtration mold according to claim 1,
A compact is manufactured by draining the water in the slurry under reduced pressure only from the filter side.
A method for producing a sputtering target of a high-purity ITO sintered body, comprising drying and degreasing the obtained ITO molded body and then firing.
このスラリーを請求項２に記載の濾過式成形型に注入し、
フィルター面側からのみスラリー中の水分を減圧排水して成形体を製作し、
得られたＩＴＯ成形体を乾燥脱脂後、焼成すること
を特徴とする肉厚差を有するＩＴＯ焼結体スパッタリングターゲットの製造方法。Prepare a slurry composed of indium oxide powder, tin oxide powder, ion-exchanged water and organic additives,
Injecting the slurry into the filtration mold according to claim 2,
A compact is manufactured by draining the water in the slurry under reduced pressure only from the filter side.
A method for producing an ITO sintered body sputtering target having a thickness difference, wherein the obtained ITO molded body is dried and degreased and then fired.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24490098A JP3571540B2 (en) | 1998-02-04 | 1998-08-31 | Filtration mold and method for producing ceramic sintered body using the mold |
| TW088101590A TW548256B (en) | 1998-02-04 | 1999-02-02 | Filtration-type mold and method for producing ceramic sintered body using the mold |
| KR10-1999-0003841A KR100453621B1 (en) | 1998-02-04 | 1999-02-04 | Filtration forming mold and method for producing ceramics sintered body using the same |
| CN99100765A CN1121358C (en) | 1998-02-04 | 1999-02-04 | Filtration-type mold and mehtod for producing ceramic sintered body using the mold |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2325798 | 1998-02-04 | ||
| JP10-23257 | 1998-02-04 | ||
| JP24490098A JP3571540B2 (en) | 1998-02-04 | 1998-08-31 | Filtration mold and method for producing ceramic sintered body using the mold |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2004006953A Division JP2004155202A (en) | 1998-02-04 | 2004-01-14 | Filter type mold and method for manufacturing ceramic sintered body using the mold |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH11286002A JPH11286002A (en) | 1999-10-19 |
| JP3571540B2 true JP3571540B2 (en) | 2004-09-29 |
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| Application Number | Title | Priority Date | Filing Date |
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| JP24490098A Expired - Lifetime JP3571540B2 (en) | 1998-02-04 | 1998-08-31 | Filtration mold and method for producing ceramic sintered body using the mold |
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| JP (1) | JP3571540B2 (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2349601A (en) * | 1999-05-07 | 2000-11-08 | Secr Defence | Boron carbide cast bodies |
| TWI385139B (en) * | 2005-02-01 | 2013-02-11 | Tosoh Corp | A sintered body, a sputtering target and a forming die, and a sintered body manufacturing method using the same |
| CN101142066A (en) * | 2005-03-14 | 2008-03-12 | 皇家飞利浦电子股份有限公司 | Method of producing a component with a surface structure, ceramic component and application of such a method |
| JP4295811B1 (en) | 2008-09-17 | 2009-07-15 | 三井金属鉱業株式会社 | Zinc oxide target |
| JP2011179056A (en) * | 2010-02-26 | 2011-09-15 | Taiheiyo Cement Corp | Sputtering target |
| JP5497479B2 (en) * | 2010-02-26 | 2014-05-21 | 太平洋セメント株式会社 | Sputtering target |
| SG11201504191RA (en) | 2011-06-08 | 2015-07-30 | Semiconductor Energy Lab | Sputtering target, method for manufacturing sputtering target, and method for forming thin film |
| US9885108B2 (en) * | 2012-08-07 | 2018-02-06 | Semiconductor Energy Laboratory Co., Ltd. | Method for forming sputtering target |
| US10557192B2 (en) | 2012-08-07 | 2020-02-11 | Semiconductor Energy Laboratory Co., Ltd. | Method for using sputtering target and method for forming oxide film |
| JP6141777B2 (en) | 2013-02-28 | 2017-06-07 | 株式会社半導体エネルギー研究所 | Method for manufacturing semiconductor device |
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| JPH11286002A (en) | 1999-10-19 |
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