JP2004000504A - Intraoral appliance and ion implantation method to intraoral appliance - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To exhibit superior antimicrobial performance for a long period by implanting antimicrobial ions to the inside of a complicated three-dimensional intraoral appliance in a short time. <P>SOLUTION: The intraoral appliance partially or wholly implants fluorine ions or antimicrobial metal ions having an antimicrobial activity to a part or all of the surface of a metal or a ceramic material. Parts where the fluorine or the antimicrobial ions are implanted are the surface of an artificial tooth 11, the surface of a denture base 12, the surface of a retaining appliance 19, the surface of an occlusion guiding appliance 13, the surface of an orthodontic appliance 14, and a superstructure to cover an artificial dental root 21. An ion implantation method to the intraoral appliance includes that a conductive material 7 having conductivity and clearances for letting the ions to pass is disposed outside the intraoral appliance, the conductive material 7 is electrically connected to a holder 6 having the intraoral appliance set therein, plasma is formed in the periphery of the intraoral appliance 1, and pulsed high voltage is impressed on the intraoral appliance to implant the antimicrobial ions from the surface. <P>COPYRIGHT: (C)2004,JPO

Description

【００２９】
ただし、フッ素元素濃度は，Ｘ線光電子分光分析装置（ＸＰＳ：Ｘ−ｒａｙ　Ｐｈｏｔｏ−ｅｌｅｃｔｒｏｎ　Ｓｐｅｃｔｒｏｍｅｔｅｒ）により、真空中でＡｒスパッタして表面に付着した炭素を落とした後に測定した。
【００３０】
［実施例２］
ステンレスと比較してチタン製の口腔内装置にイオン注入する。チタンには純チタンを使用する。ただ、チタンには、純チタン以外のチタン合金も使用できる。チタンの口腔内装置も、ステンレスと同じように用途に適した形状に加工して使用されるが、形状にかかわらず表面にイオン注入されるので、この実施例においても、ステンレスと同じように、口腔内装置を、長さ１０ｍｍ、幅１０ｍｍ、厚さ１ｍｍの板状とする。チタンにフッ素イオンを注入するために、ＡｒとＦ_２の混合ガスを用いる。この混合ガスには、カーボンや硫黄等の不純物濃度の少ないものがよい。このガス中のＦ_２含有量は５％で、多くはＡｒであるが、Ａｒガスは不活性ガスであるので、たとえフッ素と同時にＡｒがイオン注入されても、すぐに気化して残存しない。ＰＢＩＩ装置を使用して、Ａｒ＋Ｆ_２混合ガスを使用するイオン注入の条件は、Ａｒ＋Ｆ_２混合ガス流量を７０ＳＣＣＭ、チャンバー内ガス圧を１．０Ｐａ、誘引パルス負電圧を１〜２０ｋＶの間で変化させ、繰り返しパルス数を１０００ｐｕｌｓｅｓ／ｓｅｃ、パルス幅を１０μｓとし、注入時間を６０分としてイオン注入する。
【００３１】
この装置でイオン注入されたチタンをＳＩＭＳ分析してフッ素濃度を検出すると、図８のグラフに示すように変化する。このグラフは、チタンもステンレスと同じようにフッ素イオンが注入されるが、ステンレスよりもチタンの方が僅かに多くのフッ素が注入され、表面でのフッ素濃度（ＣＰＳ）が約１０^４オーダとなり、内部に向かって濃度が低下する。パルス電圧を２０ｋＶとし、注入時間を６０分とすると、表面から約６０ｎｍまでの深さで約１０^３〜１０^４オーダでフッ素が注入され、注入エネルギーが高いほど、深く多くフッ素が注入される。さらに、この実施例で得られた口腔内装置の細菌付着を測定すると、フッ素イオン注入しない口腔内装置では８．７×１０^４ｃｏｕｎｔｓであったが、５ｋｅＶと１０ｋｅＶで６０分フッ素イオン注入すると、それぞれ２．８×１０^４ｃｏｕｎｔｓ、２．１×１０^４ｃｏｕｎｔｓと減少して、細菌の付着性が抑制された。
【００３２】
［実施例３］
導電性材料と比較のため、合成樹脂製の口腔内装置にイオン注入する。イオン注入する合成樹脂には、ポリメチルメタクリレート樹脂（ＰＭＭＡ）を使用する。ただし、口腔内装置には、ポリメチルメタクリレート樹脂（ＰＭＭＡ）以外も使用されるので、このポリメチルメタクリレート樹脂以外の合成樹脂の口腔内装置も、以下に示すようにしてイオン注入できる。さらに、口腔内装置の合成樹脂も、用途に適した形状に加工して使用されるが、形状にかかわらず表面にイオン注入されるので、この実施例においても、合成樹脂製の口腔内装置を、長さ１０ｍｍ、幅１０ｍｍ、厚さ１ｍｍの板状とする。合成樹脂製の口腔内装置の表面にＰＢＩＩ装置を使用して、負電圧の繰り返しパルス数を１０００ｐｕｌｓｅｓ／ｓｅｃ、パルス幅１０μｓで、ガス圧は１．０Ｐａで、電圧は５、１０ｋＶ、時間は６０分でＣＦ_４ガスを用いてフッ素イオンの注入を行う。
【００３３】
この装置でイオン注入された合成樹脂をＳＩＭＳ分析してフッ素濃度を検出すると、図９のグラフに示すように変化する。このグラフから、パルス電圧を５ｋＶとし、注入時間を６０分とすると、表面でのフッ素濃度（ＣＰＳ）は約１０^４オーダとなって内部に向かって次第に低下し、パルス電圧を１０ｋＶとし、注入時間を６０分とすると、イオン注入される濃度が低くなる。したがって、合成樹脂製の口腔内装置は絶縁材なので、高エネルギーではチャージアップが大きくなるため、注入エネルギーは約５ｋｅＶ程度の場合に多くフッ素が注入される。
【００３４】
ところで、合成樹脂のような絶縁材の口腔内装置にイオン注入すると、図１０に示すように、プラスに帯電されたフッ素イオンにより口腔内装置１がチャージアップされる。チャージアップされてプラスに帯電された口腔内装置１は、イオンを反発してイオン注入を妨害する。この弊害は、図１１に示すように、口腔内装置１の外側に導電性があってイオンの通過隙間がある導電材７を設け、この導電材７を、口腔内装置１をセットしているホルダー６に接続してホルダー６と同電位にして解消できる。この装置は、ホルダー６と導電材７である金属網の空間でホローカソード放電によって中和用プラズマが生成される。この中和用プラズマ中の電子によって、絶縁物表面に蓄積される注入イオンや２次電子放出による電荷の大部分が中和されるので、チャージアップはほとんど無くなり、抵抗なくプラスイオンを注入できる。中和用プラズマは、ホルダー６と同電位であるので、中和用プラズマ中にあるイオンは注入されず、金属網の外側に形成されるイオンシースからメッシュを通過したイオンが口腔内装置１に注入される。そのため、イオン注入エネルギーは変化しない。導電材７には、たとえばチタン網やステンレス網等の金属網を使用する。とくに、金属網にチタン網を使用してイオン注入した絶縁材である口腔内装置は、細菌付着量が無処理材の１．６×１０^５ｃｏｕｎｔｓに対し、５ｋｅＶ６０分注入材では１．０×１０^３ｃｏｕｎｔｓとなり、約１／１００に著しく低減できる。それは、チタン網がフッ素イオン注入時にスパッタされ、フッ素と同時にチタンイオンが口腔内装置に注入されるため、チタンによっても菌付着性が抑制されるからである。
【００３５】
図１１に示すように、金属網を設けたＰＢＩＩ装置でイオン注入された合成樹脂製の口腔内装置をＳＩＭＳ分析してフッ素濃度を検出すると、図１２のグラフに示すように、より効率よく口腔内装置の深くまでフッ素が注入される。このグラフは、パルス電圧を５ｋＶとし、注入時間を６０分とすると、表面でのフッ素濃度（ＣＰＳ）は約１０^４オーダとなって内部に向かって少しずつ低下し、パルス電圧を１０ｋＶとし、注入時間を６０分とすると、イオンの注入される濃度が低くなる。したがって、合成樹脂製の口腔内装置は、注入エネルギーが約５ｋｅＶ程度の場合に深く多くフッ素が注入される。この実施例で得られた口腔内装置の細菌付着を測定すると、フッ素イオン注入しない口腔内装置の１．６×１０^５ｃｏｕｎｔｓに比較して、５．４×１０^３ｃｏｕｎｔｓとなり、細菌の付着性が抑制される。とくに、金属網を使用してイオン注入した口腔内装置は、２．１×１０^３ｃｏｕｎｔｓとなり、細菌の付着量が効果的に抑制される。
【００３６】
［実施例４］
別の絶縁材料としてシリコンラバー製の口腔内装置にイオン注入する。この実施例においても、シリコンラバー製の口腔内装置を、長さ１０ｍｍ、幅１０ｍｍ、厚さ１ｍｍの板状とする。シリコンラバー製の口腔内装置の表面にＰＢＩＩ装置を使用して、負電圧の繰り返しパルス数を１０００ｐｕｌｓｅｓ／ｓｅｃ、パルス幅１０μｓで、ガス圧は１．０Ｐａで、電圧は３〜２０ｋＶ、時間は６０分でＣＦ_４ガスを用いてフッ素イオンの注入を行う。この実施例で得られた口腔内装置の細菌付着を測定すると１．８×１０^４ｃｏｕｎｔｓで、フッ素イオン注入しないシリコンラバーの口腔内装置の３．８×１０^６ｃｏｕｎｔｓに比較して、細菌の付着性が抑制された。
【００３７】
［実施例５］
さらに、イオン注入するガスの種類を替えてシリコンラバー製の口腔内装置にイオン注入する。この実施例においても、シリコンラバー製の口腔内装置を、長さ１０ｍｍ、幅１０ｍｍ、厚さ１ｍｍの板状とする。シリコンラバー製の口腔内装置の表面にＰＢＩＩ装置を使用して、Ａｒ＋Ｆ_２混合ガス流量は７０ＳＣＣＭ、チャンバー内ガス圧は１．０Ｐａ、誘引パルス負電圧は３〜２０ｋＶ、繰り返しパルス数は１０００ｐｕｌｓｅｓ／ｓｅｃ、パルス幅は１０μｓ、イオン注入量は注入時間６０分とする。
【００３８】
以上のようにしてイオン注入された口腔内装置をＳＩＭＳ分析してフッ素濃度を検出すると、図１３に示すようになる。このグラフは、表面でのフッ素濃度（ＣＰＳ）が約１０^３オーダとなり、内部に向かって濃度が低下する。パルス電圧を２０ｋＶとし、注入時間を６０分とすると、表面から約５００ｎｍの深さまで約１０^２オーダでフッ素が注入されたが、注入時の発熱による損傷が生じたため、１０ｋｅＶ以下、特に約５ｋｅＶで注入することが望ましい。
【００３９】
さらに、図１１に示すように金属網を設けてシリコンラバー製の口腔内装置にイオン注入すると、図１４に示すように、パルス電圧を低くして深部まで注入される。とくに、パルス電圧を５ｋＶにすると内部まで多くイオンを注入できることがわかる。
【００４０】
この実施例で得られた口腔内装置の細菌付着を測定すると、無注入の口腔内装置の３．８×１０^６ｃｏｕｎｔｓに比較して、パルス電圧を約５ｋＶにしてイオン注入を多くしたものは１．３×１０^５ｃｏｕｎｔｓとなり、より細菌の付着性が抑制される。さらに、ステンレス製の金属網を設けてイオン注入したシリコンラバー製の口腔内装置は７．８×１０^４ｃｏｕｎｔｓで、細菌の付着性をより抑制できる特長がある。特に、チタン製の金属を設けてイオン注入したシリコンラバー製の口腔内装置の測定値は６．７×１０^３ｃｏｕｎｔｓとなり、細菌の付着性を約１／１００以下に著しく低減できる。
【００４１】
［実施例６］
上記の実施例はフッ素を示したが金属系イオンについても実施した。シリコンラバー製の口腔内装置に抗菌性金属であるチタンをイオン注入する。口腔内装置のシリコンラバーは実施例５と同じものを使用する。この実施例は、口腔内装置に抗菌性金属であるチタンをイオン注入するために、図１１に示すように、チタン製の金属網を設けてシリコンラバー製の口腔内装置にイオン注入する。真空チャンバー３に供給するガスは、フッ素を含まないＡｒを用いる。このＰＢＩＩ装置で抗菌性金属であるチタンをイオン注入する条件は、Ａｒガス流量を７０ＳＣＣＭ、チャンバー内ガス圧を１．０Ｐａ、誘引パルス負電圧を３〜２０ｋＶ、繰り返しパルス数を１０００ｐｕｌｓｅｓ／ｓｅｃ、パルス幅を１０μｓ、イオン注入量は注入時間６０分とする。この実施例で得られた口腔内装置の細菌付着を測定すると、パルス電圧を３ｋＶにしてイオン注入を多くしたものが２．３×１０^５ｃｏｕｎｔｓで、無注入の口腔内装置の３．８×１０^６ｃｏｕｎｔｓに比較して、より細菌の付着性が抑制される。
【００４２】
［実施例７］
シリコンラバー製に代わって、ポリメチルメタクリレート樹脂（ＰＭＭＡ）を使用する以外、実施例６と同じようにして、口腔内装置に抗菌性金属であるチタンをイオン注入する。この実施例で得られた口腔内装置の細菌付着を測定すると２．１×１０^４ｃｏｕｎｔｓで、無注入の口腔内装置の１．６×１０^５ｃｏｕｎｔｓに比較して、著しく細菌の付着性が抑制される。
【００４３】
［実施例８］
次に、立体物である口腔内装置に対してプラズマ源正面に置かれたサンプルと裏側などに置かれたサンプルが均一にイオン注入されるかどうか確認するため図５に示す設備を用いて、金属あるいは樹脂材料に対して凹凸のある状態で均一にイオン注入が出来るかどうかを図１５に示すような治具を用いて実施した。図１５は、階段状に形成したサンプルホルダー２４の段差面にサンプル２５を設置し、各段差面を遮蔽板２６で仕切って、サンプル２５が遮蔽板２６とサンプルホルダー２４で囲まれる溝の底に設置されている状態を形成して行った。
【００４４】
用いたサンプル２５は、１０ｍｍ×６０ｍｍ×１ｍｍのＳＵＳ３１６Ｌ板である。サンプルホルダー２４が階段状に形成されているため、遮蔽板２６とサンプルホルダー２４で囲まれる溝のアスペクト比が溝ごとに異なる。ここではアスペクト比を０〜５の範囲とした。アスペクト比とは、溝の深さ／溝幅のことである。アスペクト比０は、平板で溝のない状態を示している。
【００４５】
プラズマ源に対してＳＵＳ３１６Ｌサンプルを正面に配置し、溝の内部にサンプルを設置してフッ素イオン注入処理後、そのサンプル表面の元素分析を行い、フッ素元素の濃度と水に対する接触角を調べた。イオン注入条件は、チャンバー内圧力が１．０Ｐａ、注入時間６０分、誘引パルス電圧が５ｋＶ、繰り返しパルス数が１０００ｐｕｌｓｅｓ／ｓｅｃ、フッ素系ガスがＡｒ＋Ｆ_２である。その結果を表２に示す。アスペクト比が５までは３５ａｔ％以上のフッ素元素の注入ができていることが分かる。水に対する接触角は、アスペクト比５まで無処理材より有意に高く、アスペクト比が相当に大きく、いいかえると表面に相当に深い凹部があっても、凹部の底の表面から内部までイオン注入されることが分かった。
【００４６】
【表２】

【００４７】
［実施例９］
実施例８と比較するため、ＳＵＳ３１６Ｌ評価サンプルはプラズマ源に対して側面に配置して実施例８と同一条件でイオン注入処理を行った。その後、光電子分光分析法により元素分析を行い、フッ素含有量を評価した。この結果アスペクト比が０、１、２、３、４でのフッ素元素濃度は、各々４１．６ａｔ％、４１．８ａｔ％、４１．３ａｔ％、４０．２ａｔ％、３９．８ａｔ％となり、アスペクト比４まで３５ａｔ％以上のフッ素元素が注入されていた。水に対する接触角も、それぞれ、１０５度、１０２度、１００度、１０１度、９９度とアスペクト比４においても無処理材より有意に高かった。
【００４８】
［実施例１０］
実施例８と比較するため、ＳＵＳ３１６Ｌ評価サンプルはプラズマ源に対して裏面に配置して実施例８と同一条件でイオン注入処理を行った。その後、光電子分光分析法により元素分析を行いフッ素含有量を評価した。この結果、アスペクト比が０、１、２、３、４でのフッ素元素の濃度は各々４０．６ａｔ％、４０．２ａｔ％、４０．１ａｔ％、３９．２ａｔ％、３５．８ａｔ％となり、アスペクト比４まで３５ａｔ％以上のフッ素元素が注入されていた。水に対する接触角も、それぞれ、１０４、１０５、９６、９２、８５度とアスペクト比３まで無処理材より有意に高かった。
【００４９】
［実施例１１］
絶縁物に対しても凹凸のある影響を評価するため、プラズマ源に対して合成樹脂（ＰＭＭＡ）サンプルを正面に配置し、図１１に示すように金属網を設け、実施例８と同じようにして溝の内部にサンプルを設置してフッ素イオン注入後、そのサンプル表面の元素分析を行い、フッ素元素濃度と水に対する接触角を調べた。イオン注入条件は、チャンバー内圧力が１．０Ｐａ、注入時間６０分、誘引パルス電圧が５ｋＶ、繰り返しパルス数が１０００ｐｕｌｓｅｓ／ｓｅｃ、フッ素系ガスがＡｒ＋Ｆ_２である。その結果を表３に示す。この結果から、アスペクト比が５まで１０ａｔ％以上のフッ素元素が注入ができていることが分かる。水に対する接触角も、アスペクト比５と溝の深さを相当に大きくしても、無処理材より有意に高かった。
【００５０】
【表３】

【００５１】
［実施例１２］
上記と同様にプラズマ源に対してＰＭＭＡサンプルを側面に配置し、図１１に示すように金属網を設け、実施例１１と同じようにして溝の内部にサンプルを設置してイオン注入処理後、アスペクト比が０、１、２、３、４のフッ素元素の濃度は各々１１．７ａｔ％、１１．６ａｔ％、１１．２ａｔ％、１０．８ａｔ％、１０．６ａｔ％となり、アスペクト比４まで１０ａｔ％以上のフッ素元素が注入されていた。水に対する接触角も、それぞれ、１１２度、１１０度、１０８度、１０７度、１０２度とアスペクト比４と相当に深い領域まで無処理材より有意に高かった。
【００５２】
［実施例１３］
さらに上記と同様にしてプラズマ源に対してＰＭＭＡサンプルを裏面に配置し、図１１に示すように金属網を設け、実施例１１と同じようにして溝の内部にサンプルを設置してイオン注入処理後、アスペクト比が０、１、２、３でのフッ素元素濃度は各々１１．２ａｔ％、１１．１ａｔ％、１０．８ａｔ％、１０．６ａｔ％となり、アスペクト比３まで１０ａｔ％以上のフッ素元素が注入されていた。水に対する接触角も、それぞれ、１１０度、１０８度、１０５度、１０４度とアスペクト比３まで無処理材より有意に高かった。
【００５３】
以上の実施例は、口腔内装置にフッ素やチタンをイオン注入しているが、口腔内装置には、チタン以外の抗菌性金属をイオン注入して細菌の付着量を少なくすることもできる。抗菌性金属をイオン注入して口腔内装置の菌付着量を少なくできることは、図１１に示すように、抗菌性金属であるチタンからなる金属網を使用してイオン注入し、菌付着量が減少することからも明らかであるが、抗菌性金属のイオン注入は、図１６に示すように、抗菌性金属を真空チャンバー３内にプラズマとして供給する装置でも行うことができる。この装置は、抗菌性金属のプラズマを真空チャンバー３に供給するプラズマ源８を備える。プラズマ源８は、抗菌性金属であるチタン、銀、銅、亜鉛等の金属をプラズマとするパルス・アーク電源９を備える。抗菌性金属のプラズマは、フッ素のイオン注入と同じように、パルスの高電圧で加速されて口腔内装置１にイオン注入される。抗菌性金属をイオン注入する口腔内装置１は、金属または陶材である。
【００５４】
［実施例１４］
抗菌性金属イオンとして、純チタン製の口腔内装置に銀をイオン注入する。口腔内装置のチタンは実施例２と同じものを使用する。この実施例は、口腔内装置に抗菌性金属である銀をイオン注入するために、図１６に示すように、抗菌性金属のプラズマを真空チャンバー３に供給するプラズマ源８とパルス・アーク電源９を備えた装置を用い、チタン製の口腔内装置にイオン注入する。真空チャンバー３に供給するガスは、フッ素を含まないＡｒを用いる。このＰＢＩＩ装置で抗菌性金属である銀をイオン注入する条件は、Ａｒガス流量を７０ＳＣＣＭ、チャンバー内ガス圧を１．０Ｐａ、誘引パルス負電圧を３〜２０ｋＶ、繰り返しパルス数を１０００ｐｕｌｓｅｓ／ｓｅｃ、パルス幅を１０μｓ、イオン注入量は注入時間６０分とする。この実施例で得られた口腔内装置の注入深さはＳＩＭＳ分析から５０〜１００ｎｍで、細菌付着を測定すると、パルス電圧を２０ｋＶにしてイオン注入を多くしたものが１．３×１０^４ｃｏｕｎｔｓで、無注入の口腔内装置の８．７×１０^５ｃｏｕｎｔｓに比較して、より細菌の付着性が抑制される。水に対する接触角も９１度となり、無処理材の７３度より有意に高かった。
【００５５】
【発明の効果】
本発明の請求項１と請求項３の口腔内装置は、耐久性があって長期間にわたって有効な抗菌性が実現される。それは、本発明の口腔内装置が、表面にフッ素をイオン注入し、あるいは金属又は陶材等の表面部分に抗菌性金属をイオン注入しているからである。また、本発明の口腔内装置は、フッ素や抗菌性金属をイオン注入して抗菌性を実現するので、一度に大量にイオン注入できる。このため、生産性がよく、安価に多量生産できて優れた抗菌性の口腔内装置となる。とくに、歯科材料の表面にフッ素をイオン注入している口腔内装置は、単に歯科材料の表面にフッ素を塗布している口腔内装置に比較して極めて耐久性がある。それは、フッ素が表面から内部まで注入されるので、表面が摩耗しても表面にフッ素が表出するからである。また、金属や陶材の歯科材料に抗菌性金属をイオン注入している口腔内装置は、摩耗が少ないことに加えて、表面から内部に抗菌性金属をイオン注入しているので、より耐久性を向上できる特長がある。
【００５６】
さらに、本発明の請求項６のイオン注入方法は、処理したい口腔内装置をホルダーに固定して、口腔内装置の外側に導電材を配置してその周辺にプラズマを形成し、試料にパルス状の高電圧を印加しながらイオンを注入するので、立体物の形状に沿って表面に均一にイオンを注入でき、とくに複雑な３次元形状の凹部までイオン注入して有効な抗菌性を実現する。さらに、本発明のイオン注入方法は、短時間に能率よく、口腔内装置に表面から深部までイオン注入できる特長がある。口腔内装置をセットしているホルダーに導電材を電気的に接続して、抗菌材をイオン注入するからである。とくにこの方法は、絶縁材の歯科材料で構成される口腔内装置の表面にもイオン注入して抗菌性を実現する。導電材が絶縁材である口腔内装置のチャージアップを防止して、内部まで短時間で多くのイオンを注入できるからである。このようにして複雑な３次元形状の凹部まで、短時間にイオン注入して得られる口腔内装置は、極めて優れた抗菌性を実現して、菌付着量を少なくできる特長が実現される。
【図面の簡単な説明】
【図１】義歯である口腔内装置の一例を示す平面図
【図２】咬合誘導装置である口腔内装置の一例を示す平面図
【図３】歯科矯正装置である口腔内装置の一例を示す斜視図
【図４】人工歯根に被せる上部構造である口腔内装置の一例を示す断面図
【図５】本発明の一実施例にかかるイオン注入方法に使用するプラズマ型イオン注入装置の概略図
【図６】本発明のイオン注入方法でイオン注入された実施例１のステンレス製の口腔内装置のフッ素濃度を示すグラフ
【図７】実施例１で製作されたステンレス製の口腔内装置の細菌付着量を示すグラフ
【図８】本発明のイオン注入方法でイオン注入された実施例２のチタンの口腔内装置のフッ素濃度を示すグラフ
【図９】本発明のイオン注入方法でイオン注入された実施例３の合成樹脂製の口腔内装置のフッ素濃度を示すグラフ
【図１０】絶縁材の口腔内装置にイオン注入する状態を示す概略図
【図１１】口腔内装置の外側に導電材を設けてイオン注入する状態を示す概略図
【図１２】図１１に示すＰＢＩＩ装置でイオン注入された合成樹脂製の口腔内装置のフッ素濃度を示すグラフ
【図１３】本発明のイオン注入方法でイオン注入された実施例５のシリコンラバー製の口腔内装置のフッ素濃度を示すグラフ
【図１４】図１１に示すＰＢＩＩ装置でイオン注入されたシリコンラバー製の口腔内装置のフッ素濃度を示すグラフ
【図１５】アスペクト比の異なる材料へのイオン注入方法を示す概略図
【図１６】プラズマ型イオン注入装置の他の一例を示す概略図
【符号の説明】
１…口腔内装置
２…絶縁ガイシ
３…真空チャンバー
４…高圧電源
５…フィードスルー
６…ホルダー
７…導電材
８…プラズマ源
９…パルス・アーク電源
１０…義歯
１１…人工歯
１２…義歯床
１３…咬合誘導装置
１４…歯科矯正装置
１５…排気装置
１６…プラズマ源
１７…ガス供給装置
１８…制御装置
１９…維持装置
２０…義歯床
２１…人工歯根
２２…歯槽骨
２３…歯肉
２４…サンプルホルダー
２５…サンプル
２６…遮蔽板
２７…上部構造[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to an intraoral device for ion implantation and a method for manufacturing the same.
[0002]
[Prior art]
A method has been developed in which the surface of the denture base is coated with an antibacterial metal using a normal method such as vacuum deposition. However, in this method, the bonding property between the metal and the surface of the denture base is low, the metal is easily peeled off, and the antibacterial property cannot be exhibited for a long time. Therefore, a technique for ion-implanting an antibacterial metal into a synthetic resin denture base has been developed (Japanese Patent Laid-Open No. 9-10236). This denture base injects the antimicrobial metal into the surface by accelerating the antimicrobial metal at a high voltage, so that the antimicrobial metal can be injected relatively deep not only into the surface but also into the interior. However, the method of implanting using this mass-separation type ion accelerator is ion implantation from one direction, and a three-dimensional object or a complex-shaped object tends to have a portion that is not implanted even when rotated during implantation. Further, since a large number of pieces cannot be simultaneously injected and the injection time is long, the productivity is low and the cost is high.
[0003]
[Patent Document 1]
JP-A-9-10236
[0004]
On the other hand, a method of applying a fluorine compound to the surface of a denture base or the like has long been used as one method of preventing plaque adhesion, but in order to maintain this method, it is necessary to apply a drug every time, It was very difficult to maintain the effect. In addition, there have been reports of attempts to chemically prevent plaque from adhering to the surface of the dental prosthesis by using a fluorine compound on the dental prosthesis. However, only limited intraoral devices can be used with limited materials. It has not been converted.
[0005]
[Problems to be solved by the invention]
In order to solve the above-mentioned drawback, persistent antibacterial ions can be solved if the ions can be uniformly implanted so as to cover the entire surface of the intraoral device. In addition, even if an anti-bacterial ion is implanted with an insulating material that does not easily conduct electricity, positively charged ions accumulate on the surface and the surface potential increases, so that ion implantation is not performed. There was a drawback that antibacterial ions could not be implanted. Furthermore, when a large amount of ions are accumulated on the surface, the surface potential increases, and this potential rise causes a discharge breakdown, which causes damage to the intraoral apparatus due to the discharge breakdown.
[0006]
Furthermore, the conventional oral device has a disadvantage that it is difficult to realize a sufficiently satisfactory antibacterial action as an oral device since an antibacterial metal such as silver or copper is ion-implanted into a synthetic resin.
[0007]
The present invention has been developed to solve this drawback. It is an important object of the present invention to provide an inexpensive intraoral device that is durable and has antimicrobial properties for a long period of time, and a method for ion implantation into the intraoral device.
It is another important object of the present invention to provide an intraoral device which can be manufactured by using a simple device to quickly ion-inject the inside thereof, and a method of ion-implanting the intraoral device. .
Still another object of the present invention is to provide an intraoral device capable of realizing an extremely excellent antibacterial property and a method for implanting ions into the intraoral device.
Further, an important object of the present invention is to provide a method for ion implantation into an intraoral device capable of uniformly implanting one or both of fluorine and an antibacterial metal on the surface of a complicated three-dimensional intraoral device. It is in.
[0008]
[Means for Solving the Problems]
In the intraoral device according to claim 1 of the present invention, fluorine is ion-implanted into a part or the whole of the surface. The part where fluorine is ion-implanted is, for example, the surface of an artificial tooth, the surface of a denture base, the surface of a maintenance device, the surface of an occlusal guidance device, the surface of an orthodontic appliance, the surface of a superstructure placed over an artificial tooth root, and the like. .
Furthermore, the intraoral device according to claim 3 of the present invention is made of metal or porcelain, and a part or the whole of the surface of the metal or porcelain is ion-implanted with an antibacterial metal having an antibacterial action. . The antibacterial metal can be ion-implanted into the surface of an artificial tooth, the surface of a denture base, the surface of a maintenance device, the surface of an occlusal guidance device, the surface of an orthodontic appliance, the surface of a superstructure placed over an artificial tooth root, and the like. The antibacterial metal to be ion-implanted is, for example, a metal containing at least one of titanium, silver, copper, and zinc.
[0009]
Further, in the method for ion implantation into an intraoral device according to claim 6 of the present invention, a conductive material having conductivity and having a gap for passing ions is arranged outside the intraoral device, and the intraoral device is A conductive material is electrically connected to the holder that is set, plasma is formed around the intraoral device, and a pulsed high voltage is applied to the intraoral device to ion-implant the antibacterial material from the surface. Either fluorine or an antimicrobial metal or both can be used for the antimicrobial material ion implanted in this manner. Further, a metal net can be used as the conductive material, and a titanium metal net is particularly suitable for the conductive material.
[0010]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, embodiments of the present invention will be described with reference to the drawings. However, the following examples illustrate an intraoral device and a method of ion implantation into an intraoral device for embodying the technical idea of the present invention, and the present invention relates to an intraoral device and an ion implantation method. Is not specified below.
[0011]
The intraoral devices include the denture 10 shown in FIG. 1, the occlusal guidance device 13 shown in FIG. 2, the orthodontic device 14 shown in FIG. 3, and the upper structure 27 put on the artificial root 21 shown in FIG. These intraoral devices do not simply apply a fluorine compound to the surface as in the related art, but ionize fluorine from the surface into a material by converting a fluorine-based gas into plasma. In the intraoral apparatus, an antibacterial metal is made into plasma and is uniformly ion-implanted into a portion made of metal or porcelain. These intraoral devices achieve long-term antibacterial properties by ion-implanting fluorine or an antibacterial metal such as silver or titanium into a suitable depth from the surface. In these oral devices, fluorine is ion-implanted into the entire surface to have antibacterial properties on the entire surface. However, it is also possible to impart an antibacterial property by ion-implanting fluorine into only a part of the surface that requires the antibacterial property.
[0012]
The denture 10 of FIG. 1 which is an intraoral device has an artificial tooth 11 and a maintenance device 19 fixed to a denture base 12. The artificial tooth 11 is manufactured by molding metal, porcelain, or synthetic resin. In the denture 10 shown in the figure, an artificial tooth 11 is fixed to a denture base 12 made of synthetic resin, and the denture base 12 made of synthetic resin is connected by a denture base 20 made of metal. The occlusal guidance device 13 of FIG. 2 is manufactured by molding metal or synthetic resin. The orthodontic appliance 14 of FIG. 3 is also made of metal, synthetic resin, rubber, or the like. 4 is made of a metal such as titanium or an alloy, and the upper structure 27 that covers the artificial tooth 21 is made by molding metal, porcelain, or synthetic resin. Dental materials such as metals and porcelains have excellent abrasion resistance, and thus have a feature that their antibacterial properties do not decrease over a long period of time. The intraoral device can realize antibacterial properties by ion-implanting fluorine from a surface into a portion made of various dental materials. Dental materials that achieve antibacterial properties by ion implantation of fluorine include metals, porcelain, synthetic resins, and rubber.
[0013]
The upper structure 27 that covers the artificial tooth root 21 is ion-implanted with fluorine or an antibacterial metal on the surface. If the surface of the upper structure 27 is not ion-implanted, oral bacteria will propagate and cause periodontal disease and the like. As shown in FIG. 4, the artificial tooth root 21 has a tip portion embedded in the alveolar bone 22, and the embedded portion is fixed to the alveolar bone 22. The upper structure 27 is fixed on the upper end portion of the artificial tooth root 21 fixed to the alveolar bone 22 and over a protruding portion protruding from the gum. Since the artificial root 21 is embedded in the alveolar bone 22, affinity with the alveolar bone 22 is important. This is because the artificial tooth root 21 is integrated with the alveolar bone 22 and firmly fixed. Furthermore, it is important that the artificial tooth root 21 is brought into close contact with the gingiva 23 on the surface facing the gingiva 23. If a gap is formed in this portion, bacteria in the oral cavity will enter through the gap and cause alveolar pyorrhea and the like. Therefore, the artificial tooth root 21 is not ion-implanted with fluorine or an antibacterial metal. Since the artificial root 21 of FIG. 4 is not ion-implanted with fluorine or an antibacterial metal, its tip can be stably bonded to the alveolar bone 22 and firmly fixed, and on the surface facing the gingiva 23, The gingiva 23 can be adhered without any gap. Since the surface of the upper structure 27 that covers the artificial tooth root 21 is ion-implanted with fluorine or an antibacterial metal, adhesion of oral bacteria can be effectively prevented, and periodontal disease and the like can be prevented.
[0014]
A dental material made of metal or porcelain can be ion-implanted with an antibacterial metal having an antibacterial action to form an antibacterial intraoral device. Antibacterial metals to be ion-implanted are titanium, silver, copper, zinc, and the like, and titanium and silver are particularly effective. The antimicrobial metal is injected into the dental material from the surface into the ionic state.
[0015]
As a metal of a dental material into which fluorine or an antibacterial metal is ion-implanted, a gold alloy, stainless steel, a gold-silver palladium alloy, a cobalt chromium alloy, a nickel chromium alloy, titanium or the like is used. Porcelain as a dental material is obtained by molding an inorganic material containing silica, alumina, or the like into a predetermined shape and sintering it. As the synthetic resin of the dental material, polymethyl methacrylate resin or the like can be used. Silicon rubber or the like can be used as the rubber.
[0016]
An intraoral device for ion-implanting fluorine or an antibacterial metal into a surface portion is manufactured by the following device.
The intraoral device uses a plasma-based ion implantation technique (PBII method) to inject fluorine ions or an antibacterial metal into the surface portion. Intraoral devices implanted in this manner achieve extremely good antimicrobial properties. In the PBII method, as shown in FIG. 5, an intraoral device 1 to be a sample to be processed is fixed to a metal sample holder 6, plasma is formed around the sample holder 6, and a pulsed high voltage is applied to the sample. While implanting ions, ions can be uniformly implanted over the entire surface along the shape of the three-dimensional object, and ions can be implanted into a large number of intraoral devices at once.
[0017]
The PBII apparatus of FIG. 5 for performing ion implantation by the PBII method applies a negative voltage (attracting voltage) to the intraoral apparatus 1 immersed in plasma. Due to this negative voltage, a plasma sheath (ion sheath) is formed around the intraoral device 1, and an ion current flows. The ions extracted from the plasma are accelerated by the induced voltage in the sheath and injected into the surface of the intraoral device 1. In this device, ions can be implanted over the entire surface of the intraoral device 1 because the sheath covers the entire intraoral device.
[0018]
When a high voltage is continuously applied to the intraoral device 1 by the PBII method, the sheath length tends to increase with time and the injection current tends to decrease with time. In order to reduce this tendency, the timing of ion implantation and plasma generation is synchronized with a pulse. According to this method, it is possible to inject and recover the plasma lost each time by injection, to increase the plasma density, and to inject as a short sheath length suitable for the shape of the intraoral device 1. An apparatus for implanting ions into the intraoral apparatus 1 by the PBII method has a feature that the apparatus can be configured at a lower cost than an ion implantation apparatus requiring a conventional beam transport system.
[0019]
In the PBII device, a plasma source 16 and a gas supply device 17 are connected to a vacuum chamber 3 evacuated by a vacuum exhaust device 15 such as a vacuum pump, and a high-pressure power supply 4 and a pure water cooling mechanism (not shown). ), And a control device 18 is provided. In the PBII apparatus shown in the figure, in order to apply a high voltage from the upper part of the vacuum chamber 3, a high voltage power supply 4 is connected to the feedthrough 5 through a rod-shaped feedthrough 5 to apply a negative induction voltage. The feedthrough 5 is fixed to the upper surface of the vacuum chamber 3 via the insulating insulator 2. The holder 6 of the intraoral device 1 attached to the lower part of the feedthrough 5 is cooled with circulating water so that the sample is not deteriorated by heat generated by the injection current. The plasma source 16 uses an RF (Radio Frequency) gas plasma source. However, a plasma source other than an RF (Radio Frequency) gas plasma source can be used as the plasma source. This plasma source has an RF resonance frequency range of 150 to 350 kHz, a minimum operating pressure of 0.3 Pa, and a normal output of the RF gas plasma source of 200 W. Further, by controlling the optical fiber, the plasma is generated in synchronization with the induced voltage pulse. Further, the repetition frequency of the pulse normally used is set to 1000 pulses / sec.
[0020]
As a raw material for generating fluorine plasma, fluorine gas alone can be used, but a mixture or a compound gas is preferably used. This is to improve safety. The mixed gas is usually Ar + F ₂ Mixed gas, CF ₄ , C ₂ F ₆ , SF ₆ Use gas or the like. Preferably, Ar and F are free from impurities such as carbon and sulfur. ₂ Is used. F in this gas ₂ Although the content is 5% at a concentration usually used frequently, it has been confirmed that Ar gas is an inert gas, and even if it is ion-implanted simultaneously with fluorine, it is not immediately vaporized and remains. Ar + F by PBII method ₂ The condition of ion implantation using the mixed gas is Ar + F ₂ The flow rate of the mixed gas is 70 SCCM, the gas pressure in the chamber is 1.0 Pa, the negative voltage of the induced pulse is 1 to 20 kV, the number of repetition pulses is 1000 pulses / sec, the pulse width is 10 μs, and the ion implantation amount is 60 minutes.
[0021]
【Example】
[Example 1]
Ions are implanted into a stainless steel intraoral device as follows. Stainless steel (SUS316L) is used for stainless steel. However, stainless steel other than this stainless steel can also be used for stainless steel. The metal of the intraoral device is used after being processed into a shape suitable for the application. However, since the surface is ion-implanted regardless of the shape, in this embodiment, the intraoral device has a length of 10 mm and a width of 10 mm. And a plate having a thickness of 1 mm. To inject fluorine ions into stainless steel, Ar and F ₂ Is used. The mixed gas preferably has a low concentration of impurities such as carbon and sulfur. F in this gas ₂ The content is 5% and is mostly Ar, but since Ar gas is an inert gas, even if Ar is ion-implanted simultaneously with fluorine, it is immediately vaporized and does not remain. Ar + F using a PBII device ₂ The condition of ion implantation using a mixed gas is Ar + F ₂ The mixed gas flow rate was 70 SCCM, the gas pressure in the chamber was 1.0 Pa, the induced pulse negative voltage was changed between 1 and 20 kV, the number of repetition pulses was 1000 pulses / sec, the pulse width was 10 μs, and the ion implantation time was 60 minutes. inject.
[0022]
When the stainless steel ion-implanted by this apparatus is analyzed by secondary ion mass spectrometry (SIMS) to detect the fluorine concentration, it changes as shown in the graph of FIG. This graph shows that the surface has a fluorine concentration (CPS) of about 10 ³ Order, and the concentration decreases toward the inside. Assuming that the pulse voltage is 20 kV and the injection time is 60 minutes, about 10 nm at a depth of about 30 nm from the surface. ³ -10 ⁴ Fluorine is implanted on the order, and the higher the implantation energy, the deeper and more fluorine is implanted.
[0023]
However, the distribution of the implanted intraoral device is analyzed as follows. The distribution of fluorine ion-implanted into the dental material of the intraoral device in the depth direction was measured by SIMS. In this measurement, sputtering is performed using a cesium ion gun accelerated at 2 keV. The sputtering rate is calculated by dividing the depth measured using the step system after the completion of the SIMS by the sputtering time. The depth on the horizontal axis of each graph is calculated based on the sputtering time while keeping the sputtering rate constant.
[0024]
FIG. 7 shows the bacterial adhesion amount of the intraoral device made of stainless steel manufactured in this example. The intraoral device made of stainless steel without ion implantation is shown as a comparative example. The intraoral device in which fluorine ion implantation was performed at 5 keV for 60 minutes, 10 keV for 60 minutes, and 20 keV for 60 minutes showed that the FITC strength (the amount of attached bacteria) was significantly (p <0.01) higher than that of the non-implanted material. Decrease. In addition, the amount of bacteria attached was significantly (p <0.01) significantly reduced (p <0.01) in the case of 60 minutes at 10 keV and the case of 60 minutes at 20 keV, compared with the case of 60 minutes at 5 keV, and the energy was high. It is clear that the injection is more effective. Intraoral devices with excellent antibacterial properties have reduced bacterial adhesion. Therefore, it has been clarified that plaque contains many bacteria, and a decrease in the amount of bacteria attached has the same meaning as excellent antibacterial properties.
[0025]
However, the amount of attached bacteria was measured by a microfluorescence measurement method as follows.
Each sample was treated with 80% alcohol, washed with sterile PBS, and D. = 0.6. Each sample (5 pieces) is immersed in a BHI liquid medium containing mutans MT8148 (c type). After 1 hour at 37 ° C., the S.A. Mutans are fixed with 2.5% glutaraldehyde solution for 20 minutes.
Observe the bacteria adhesion state on each sample surface with a scanning electron microscope to confirm that the bacteria adhere to the monolayer.
Then, after washing each fixed sample, it was blocked and washed with 1% BSA-PBS for 30 minutes. Reaction with anti-SM antibody against mutans for 30 minutes. Next, after the sample is washed, the sample is reacted with a FITC-labeled anti-IgG antibody for 30 minutes, washed, and a vector shield is added. The sample thus prepared is measured by a micro-fluorescence photometer based on a Nikon fluorescence microscope and based on a photo count method. In the measurement, the surface of the sample on which the bacteria adhered to the monolayer was measured at five locations per sample by spot photometry (count per 0.5 sec), and the sum of the values at the five locations was defined as the measured value of one sample. The sum of the five spot areas is 4019.2 μm ² Met. The measured values of the five samples are displayed with the base subtracted, and the average value ± SD is defined as the amount of adhered bacteria.
[0026]
The wet contact angle of the stainless steel intraoral device manufactured in this example with water was measured in the atmosphere at 25 ° C. using a CA-X model manufactured by Kyowa Interface Science Co., Ltd. Although the contact angle of the stainless steel intraoral device without ion implantation was 82 degrees, the stainless steel intraoral device which performed fluorine ion implantation for 60 minutes at 5 keV, 60 minutes at 10 keV, and 60 minutes at 20 keV, In order, 105 degrees, 101 degrees, and 103 degrees, respectively, all showed significantly higher contact angles than the non-injected material. In an intraoral device having a large contact angle, water containing bacteria is repelled on the surface of the intraoral device, and bacteria are less likely to adhere. Therefore, in the present specification, the term "antibacterial" refers to not only a state of inhibiting the growth of bacteria on the surface of the oral device, that is, a state of bacteriostasis or sterilization, but also increasing the contact angle of the surface to increase dental caries and teeth. It is used in a broad sense including a state in which the adhesion of periphytes and the like is suppressed and the growth of the bacteria is substantially suppressed.
[0027]
Elemental analysis was performed on the surface of the intraoral device made of stainless steel manufactured in this example by photoelectron spectroscopy, and the fluorine element concentration is shown in Table 1. An intraoral device made of stainless steel without ion implantation is also shown as a comparative example. When fluorine ion implantation was performed at 5 keV for 60 minutes and at 10 keV for 60 minutes, the concentration of elemental fluorine on the sample surface was about 40 at%, and was not detected in the non-implanted material.
[0028]
[Table 1]

[0029]
However, the concentration of elemental fluorine was measured using an X-ray photo-electron spectrometer (XPS) after Ar sputtering was performed in vacuum to remove carbon adhering to the surface.
[0030]
[Example 2]
Ion implantation into a titanium intraoral device compared to stainless steel. Pure titanium is used for titanium. However, titanium alloys other than pure titanium can also be used. The intraoral device of titanium is also used after being processed into a shape suitable for the use similarly to stainless steel, but is ion-implanted on the surface regardless of the shape. The intraoral device is a plate having a length of 10 mm, a width of 10 mm, and a thickness of 1 mm. To implant fluorine ions into titanium, Ar and F ₂ Is used. The mixed gas preferably has a low concentration of impurities such as carbon and sulfur. F in this gas ₂ The content is 5% and is mostly Ar, but since Ar gas is an inert gas, even if Ar is ion-implanted simultaneously with fluorine, it is immediately vaporized and does not remain. Ar + F using a PBII device ₂ The condition of ion implantation using a mixed gas is Ar + F ₂ The mixed gas flow rate was 70 SCCM, the gas pressure in the chamber was 1.0 Pa, the induced pulse negative voltage was changed between 1 and 20 kV, the number of repetition pulses was 1000 pulses / sec, the pulse width was 10 μs, and the ion implantation time was 60 minutes. inject.
[0031]
When the concentration of fluorine is detected by SIMS analysis of titanium ion-implanted by this apparatus, the concentration changes as shown in the graph of FIG. This graph shows that titanium is implanted with fluorine ions in the same manner as stainless steel, but titanium is implanted with slightly more fluorine than stainless steel, and the fluorine concentration (CPS) at the surface is about 10%. ⁴ Order, and the concentration decreases toward the inside. Assuming that the pulse voltage is 20 kV and the injection time is 60 minutes, a depth of about 10 nm from the surface to about 60 nm is obtained. ³ -10 ⁴ Fluorine is implanted on the order, and the higher the implantation energy, the deeper and more fluorine is implanted. Furthermore, when the bacterial adhesion of the intraoral device obtained in this example was measured, the intraoral device without fluorine ion implantation was 8.7 × 10 ⁴ However, when fluorine ions were implanted at 5 keV and 10 keV for 60 minutes, 2.8 × 10 ⁴ counts, 2.1 × 10 ⁴ counts, and the bacterial adhesion was suppressed.
[0032]
[Example 3]
For comparison with the conductive material, ions are implanted into an intraoral device made of synthetic resin. Polymethyl methacrylate resin (PMMA) is used as the synthetic resin for ion implantation. However, since other than the polymethyl methacrylate resin (PMMA) is used for the intraoral device, an intraoral device of a synthetic resin other than the polymethyl methacrylate resin can also be ion-implanted as described below. Further, the synthetic resin of the intraoral device is also used after being processed into a shape suitable for the application, but the surface is ion-implanted regardless of the shape. , 10 mm long, 10 mm wide, and 1 mm thick. Using a PBII device on the surface of a synthetic resin intraoral device, the number of repetition pulses of a negative voltage is 1000 pulses / sec, the pulse width is 10 μs, the gas pressure is 1.0 Pa, the voltage is 5, 10 kV, and the time is 60. Min in CF ₄ Fluorine ions are implanted using a gas.
[0033]
When the concentration of fluorine is detected by SIMS analysis of the synthetic resin ion-implanted by this apparatus, the concentration changes as shown in the graph of FIG. From this graph, assuming that the pulse voltage is 5 kV and the injection time is 60 minutes, the fluorine concentration (CPS) on the surface is about 10 ⁴ If the pulse voltage is set to 10 kV and the implantation time is set to 60 minutes, the concentration for ion implantation is reduced. Therefore, since the intraoral device made of synthetic resin is an insulating material, the charge-up becomes large at high energy, so that a large amount of fluorine is injected when the injection energy is about 5 keV.
[0034]
By the way, when ions are implanted into an intraoral device made of an insulating material such as a synthetic resin, as shown in FIG. 10, the intraoral device 1 is charged up by positively charged fluorine ions. The intraoral device 1 that has been charged up and positively charged repels ions and hinders ion implantation. As shown in FIG. 11, as shown in FIG. 11, a conductive material 7 having conductivity and having a gap for passing ions is provided outside the intraoral device 1, and the conductive material 7 is set to the intraoral device 1. By connecting to the holder 6, the same potential as the holder 6 can be eliminated. In this apparatus, neutralizing plasma is generated by hollow cathode discharge in the space between the holder 6 and the metal net as the conductive material 7. The electrons in the neutralizing plasma neutralize most of the injected ions accumulated on the insulator surface and the majority of the charges due to secondary electron emission, so that charge-up is almost eliminated, and positive ions can be injected without resistance. Since the neutralizing plasma is at the same potential as the holder 6, the ions in the neutralizing plasma are not implanted, and the ions that have passed through the mesh from the ion sheath formed outside the metal mesh are transmitted to the intraoral device 1. Injected. Therefore, the ion implantation energy does not change. As the conductive material 7, a metal net such as a titanium net or a stainless steel net is used. In particular, the intraoral device, which is an insulating material ion-implanted using a titanium net as a metal net, has a bacterial adhesion of 1.6 × 10 ⁵ counts, 1.0 × 10 5 ³ counts, which can be significantly reduced to about 1/100. This is because the titanium net is sputtered at the time of fluorine ion injection, and titanium ions are injected into the intraoral apparatus at the same time as fluorine, so that the bacterial adhesion is also suppressed by titanium.
[0035]
As shown in FIG. 11, SIMS analysis of the intraoral device made of synthetic resin ion-implanted with a PBII device provided with a metal net detects the fluorine concentration, and as shown in the graph of FIG. Fluorine is injected deep into the internal device. This graph shows that when the pulse voltage is 5 kV and the injection time is 60 minutes, the fluorine concentration (CPS) on the surface is about 10 ⁴ If the pulse voltage is 10 kV and the injection time is 60 minutes, the concentration at which ions are implanted becomes low. Therefore, in an intraoral device made of synthetic resin, fluorine is injected deeply and a lot when the injection energy is about 5 keV. Bacterial adhesion of the intraoral device obtained in this example was measured. ⁵ 5.4 × 10 compared to counts ³ counts, and bacterial adhesion is suppressed. In particular, an intraoral device implanted using a metal mesh is 2.1 × 10 ³ counts, and the amount of attached bacteria is effectively suppressed.
[0036]
[Example 4]
As another insulating material, ions are implanted into an intraoral device made of silicon rubber. Also in this embodiment, the intraoral device made of silicone rubber is formed into a plate having a length of 10 mm, a width of 10 mm, and a thickness of 1 mm. Using a PBII device on the surface of an intraoral device made of silicon rubber, the number of repetition pulses of a negative voltage is 1000 pulses / sec, the pulse width is 10 μs, the gas pressure is 1.0 Pa, the voltage is 3 to 20 kV, and the time is 60. Min in CF ₄ Fluorine ions are implanted using a gas. Bacterial adhesion of the intraoral device obtained in this example was measured to be 1.8 × 10 ⁴ counts, 3.8x10 of silicone rubber oral device without fluorine ion implantation ⁶ Bacterial adhesion was suppressed as compared to counts.
[0037]
[Example 5]
Further, the type of gas to be ion-implanted is changed and the ion is implanted into an intraoral device made of silicon rubber. Also in this embodiment, the intraoral device made of silicone rubber is formed into a plate having a length of 10 mm, a width of 10 mm, and a thickness of 1 mm. Ar + F using a PBII device on the surface of an intraoral device made of silicon rubber ₂ The flow rate of the mixed gas is 70 SCCM, the gas pressure in the chamber is 1.0 Pa, the negative voltage of the induced pulse is 3 to 20 kV, the number of repetition pulses is 1000 pulses / sec, the pulse width is 10 μs, and the ion implantation amount is 60 minutes.
[0038]
FIG. 13 shows the result of SIMS analysis of the intraoral device into which the ions have been implanted as described above to detect the fluorine concentration. This graph shows that the fluorine concentration (CPS) on the surface is about 10 ³ Order, and the concentration decreases toward the inside. Assuming that the pulse voltage is 20 kV and the injection time is 60 minutes, about 10 nm is reached from the surface to a depth of about 500 nm. ² Although fluorine was implanted in the order, damage due to heat generation at the time of implantation occurred. Therefore, it is desirable to implant fluorine at 10 keV or less, particularly about 5 keV.
[0039]
Further, when a metal mesh is provided as shown in FIG. 11 and ions are implanted into an intraoral device made of silicon rubber, as shown in FIG. 14, the pulse voltage is lowered and the ions are implanted deeply. In particular, when the pulse voltage is set to 5 kV, it can be seen that many ions can be implanted into the inside.
[0040]
Bacterial adherence of the oral device obtained in this example was determined to be 3.8 × 10 ⁶ In comparison with the counts, the pulse voltage was about 5 kV and the ion implantation was increased. ⁵ counts, and the adhesion of bacteria is further suppressed. Furthermore, an intraoral device made of silicon rubber implanted with a metal net made of stainless steel and ion-implanted is 7.8 × 10 ⁴ The counts have a feature that bacterial adhesion can be further suppressed. In particular, the measured value of an intraoral device made of silicon rubber implanted with titanium metal and ion-implanted is 6.7 × 10 ³ counts, and the bacterial adhesion can be significantly reduced to about 1/100 or less.
[0041]
[Example 6]
Although the above example shows fluorine, it was also carried out for metal ions. Titanium, which is an antibacterial metal, is ion-implanted into an oral device made of silicon rubber. The same silicone rubber as in the fifth embodiment is used for the intraoral device. In this embodiment, in order to ion-implant titanium which is an antibacterial metal into an oral device, as shown in FIG. 11, a metal net made of titanium is provided and ion-implanted into an oral device made of silicon rubber. As a gas supplied to the vacuum chamber 3, Ar containing no fluorine is used. The conditions for ion-implanting titanium, which is an antibacterial metal, with this PBII apparatus are as follows: Ar gas flow rate is 70 SCCM, chamber gas pressure is 1.0 Pa, attracting pulse negative voltage is 3 to 20 kV, repetition pulse number is 1000 pulses / sec, pulse is The width is 10 μs, and the ion implantation amount is 60 minutes. When the bacterial adhesion of the intraoral device obtained in this example was measured, the pulse voltage was set to 3 kV and the ion implantation was increased to 2.3 × 10 ⁵ counts, 3.8 x 10 ⁶ Bacterial adhesion is more suppressed as compared with counts.
[0042]
[Example 7]
Titanium, which is an antibacterial metal, is ion-implanted into an intraoral device in the same manner as in Example 6, except that polymethyl methacrylate resin (PMMA) is used instead of silicon rubber. Bacterial adherence of the intraoral device obtained in this example was measured to be 2.1 × 10 ⁴ counts, 1.6 x 10 for non-injected buccal device ⁵ Bacterial adhesion is significantly suppressed as compared with counts.
[0043]
Example 8
Next, using the equipment shown in FIG. 5 to confirm whether the sample placed in front of the plasma source and the sample placed on the back side or the like are uniformly ion-implanted with respect to the intraoral device which is a three-dimensional object, Whether or not ions can be uniformly implanted into a metal or resin material in an uneven state was determined using a jig as shown in FIG. FIG. 15 shows that a sample 25 is placed on a stepped surface of a sample holder 24 formed in a step shape, and each stepped surface is partitioned by a shielding plate 26, and the sample 25 is placed at the bottom of a groove surrounded by the shielding plate 26 and the sample holder 24. It was carried out by forming the installed state.
[0044]
The sample 25 used is a SUS316L plate of 10 mm × 60 mm × 1 mm. Since the sample holder 24 is formed stepwise, the aspect ratio of the groove surrounded by the shielding plate 26 and the sample holder 24 differs for each groove. Here, the aspect ratio was in the range of 0 to 5. The aspect ratio is the depth / groove width of the groove. An aspect ratio of 0 indicates a flat plate with no grooves.
[0045]
The SUS316L sample was placed in front of the plasma source, the sample was placed inside the groove, and after the fluorine ion implantation treatment, the surface of the sample was subjected to elemental analysis to check the concentration of the elemental fluorine and the contact angle with water. The ion implantation conditions are as follows: chamber pressure is 1.0 Pa, implantation time is 60 minutes, attracting pulse voltage is 5 kV, number of repetition pulses is 1000 pulses / sec, and fluorine gas is Ar + F. ₂ It is. Table 2 shows the results. It can be seen that up to an aspect ratio of 5, elemental fluorine of at least 35 at% can be implanted. The contact angle to water is significantly higher than that of the untreated material up to an aspect ratio of 5, and the aspect ratio is considerably large. In other words, even if there is a considerably deep concave portion on the surface, ions are implanted from the bottom surface of the concave portion to the inside. I found out.
[0046]
[Table 2]

[0047]
[Example 9]
For comparison with Example 8, the SUS316L evaluation sample was placed on the side of the plasma source and subjected to ion implantation under the same conditions as Example 8. Thereafter, elemental analysis was performed by photoelectron spectroscopy to evaluate the fluorine content. As a result, the fluorine element concentrations at aspect ratios of 0, 1, 2, 3, and 4 are 41.6 at%, 41.8 at%, 41.3 at%, 40.2 at%, and 39.8 at%, respectively. Up to 4, 35 at% or more of elemental fluorine has been implanted. The contact angles to water were 105, 102, 100, 101, and 99 degrees, respectively, and the aspect ratio 4 was significantly higher than the untreated material.
[0048]
[Example 10]
For comparison with Example 8, the SUS316L evaluation sample was placed on the back surface with respect to the plasma source, and was subjected to ion implantation under the same conditions as Example 8. Thereafter, elemental analysis was performed by photoelectron spectroscopy to evaluate the fluorine content. As a result, the concentration of elemental fluorine at an aspect ratio of 0, 1, 2, 3, 4 was 40.6 at%, 40.2 at%, 40.1 at%, 39.2 at%, and 35.8 at%, respectively. Up to a ratio of 4, at least 35 at% of elemental fluorine has been implanted. The contact angles to water were 104, 105, 96, 92, and 85 degrees, respectively, and were significantly higher than the untreated material up to an aspect ratio of 3.
[0049]
[Example 11]
A synthetic resin (PMMA) sample was placed in front of the plasma source to evaluate the unevenness of the insulator, and a metal net was provided as shown in FIG. After the sample was set inside the groove and fluorine ions were implanted, the surface of the sample was subjected to elemental analysis to check the fluorine element concentration and the contact angle with water. The ion implantation conditions are as follows: chamber pressure is 1.0 Pa, implantation time is 60 minutes, attracting pulse voltage is 5 kV, number of repetition pulses is 1000 pulses / sec, and fluorine gas is Ar + F. ₂ It is. Table 3 shows the results. From this result, it can be understood that the fluorine element having an aspect ratio of up to 5 and at least 10 at% can be implanted. The contact angle to water was also significantly higher than the untreated material, even if the aspect ratio was 5 and the groove depth was considerably large.
[0050]
[Table 3]

[0051]
[Example 12]
A PMMA sample was placed on the side of the plasma source in the same manner as described above, a metal net was provided as shown in FIG. 11, and the sample was placed inside the groove in the same manner as in Example 11 to perform ion implantation. The concentrations of the fluorine elements having aspect ratios of 0, 1, 2, 3, and 4 are 11.7 at%, 11.6 at%, 11.2 at%, 10.8 at%, and 10.6 at%, respectively. % Or more elemental fluorine was implanted. The contact angles with water were 112, 110, 108, 107, and 102 degrees, respectively, and were significantly higher than the untreated material up to a considerably deep area with an aspect ratio of 4.
[0052]
Example 13
Further, the PMMA sample was placed on the back side of the plasma source in the same manner as described above, a metal net was provided as shown in FIG. 11, and the sample was placed inside the groove in the same manner as in Example 11 to perform ion implantation. Thereafter, the fluorine element concentrations at the aspect ratios of 0, 1, 2, and 3 are 11.2 at%, 11.1 at%, 10.8 at%, and 10.6 at%, respectively. Had been injected. The contact angles to water were 110, 108, 105, and 104 degrees, respectively, and were significantly higher than the untreated material up to an aspect ratio of 3.
[0053]
In the above embodiment, fluorine or titanium is ion-implanted into the oral device, but an antibacterial metal other than titanium may be ion-implanted into the oral device to reduce the amount of bacteria attached. The fact that the amount of bacteria attached to the oral device can be reduced by ion-implanting the antibacterial metal is shown in FIG. 11 by reducing the amount of bacteria attached by ion implantation using a metal net made of titanium, which is an antibacterial metal. As is clear from the above, the ion implantation of the antibacterial metal can also be performed by a device for supplying the antibacterial metal as plasma into the vacuum chamber 3 as shown in FIG. The apparatus includes a plasma source 8 that supplies a plasma of an antibacterial metal to the vacuum chamber 3. The plasma source 8 includes a pulse arc power supply 9 that uses a metal such as titanium, silver, copper, or zinc, which is an antibacterial metal, as a plasma. The plasma of the antibacterial metal is accelerated by a pulsed high voltage and is ion-implanted into the intraoral apparatus 1 in the same manner as the fluorine ion implantation. The intraoral device 1 for ion-implanting an antibacterial metal is a metal or a porcelain.
[0054]
[Example 14]
As antibacterial metal ions, silver is ion-implanted into an intraoral device made of pure titanium. The same titanium as in the second embodiment is used for the intraoral device. In this embodiment, as shown in FIG. 16, a plasma source 8 for supplying a plasma of an antibacterial metal to a vacuum chamber 3 and a pulsed arc power supply 9 for ion-implanting silver as an antibacterial metal into an intraoral device. Is implanted into a titanium intraoral device using a device equipped with As a gas supplied to the vacuum chamber 3, Ar containing no fluorine is used. The conditions for ion-implanting silver as an antibacterial metal in this PBII apparatus are as follows: Ar gas flow rate is 70 SCCM, chamber gas pressure is 1.0 Pa, attracting pulse negative voltage is 3 to 20 kV, repetition pulse number is 1000 pulses / sec, pulse is The width is 10 μs, and the ion implantation amount is 60 minutes. The injection depth of the intraoral device obtained in this example was 50 to 100 nm from SIMS analysis, and when bacterial adhesion was measured, 1.3 × 10 5 was obtained by increasing the ion implantation with a pulse voltage of 20 kV. ⁴ counts, 8.7 × 10 ⁵ Bacterial adhesion is more suppressed as compared with counts. The contact angle with water was also 91 degrees, which was significantly higher than 73 degrees of the untreated material.
[0055]
【The invention's effect】
The intraoral device according to claims 1 and 3 of the present invention is durable and realizes effective antibacterial properties over a long period of time. This is because the intraoral device of the present invention ion-implants fluorine into the surface, or ion-implants antibacterial metal into the surface of metal or porcelain. Further, the intraoral device of the present invention realizes antibacterial properties by ion-implanting fluorine or an antibacterial metal, so that a large amount of ions can be implanted at one time. For this reason, a highly antibacterial oral device with good productivity, mass production at low cost, and excellent properties can be obtained. In particular, an oral device that implants fluorine into the surface of a dental material is much more durable than an oral device that simply applies fluorine to the surface of a dental material. This is because fluorine is injected from the surface to the inside, so that even if the surface is worn, fluorine is exposed on the surface. In addition, the intraoral device that implants antibacterial metal into metal and porcelain dental materials is less durable and more durable because the antibacterial metal is implanted from the surface into the interior. There is a feature that can be improved.
[0056]
Further, in the ion implantation method according to claim 6 of the present invention, the intraoral device to be processed is fixed to the holder, a conductive material is arranged outside the intraoral device, plasma is formed around the intraoral device, and the sample is pulsed. The ions are implanted while applying a high voltage, so that the ions can be uniformly implanted on the surface along the shape of the three-dimensional object, and the effective antibacterial properties can be realized by implanting the ions particularly into the complicated three-dimensional concave portions. Further, the ion implantation method of the present invention has a feature that the intraoral device can be ion-implanted from the surface to the deep portion efficiently in a short time. This is because the conductive material is electrically connected to the holder in which the intraoral device is set, and the antibacterial material is ion-implanted. In particular, this method achieves antibacterial properties by ion-implanting the surface of an intraoral device composed of an insulating dental material. This is because charge-up of the intraoral device in which the conductive material is an insulating material is prevented, and a large amount of ions can be implanted into the intraoral device in a short time. An intraoral device obtained by ion-implanting a complex three-dimensional concave portion in a short time in this way realizes extremely excellent antibacterial properties and has a feature that the amount of adhered bacteria can be reduced.
[Brief description of the drawings]
FIG. 1 is a plan view showing an example of an intraoral device that is a denture.
FIG. 2 is a plan view showing an example of an intraoral device which is an occlusal guidance device.
FIG. 3 is a perspective view showing an example of an intraoral device which is an orthodontic device.
FIG. 4 is a cross-sectional view showing an example of an intraoral device as an upper structure to be placed on an artificial tooth root.
FIG. 5 is a schematic diagram of a plasma-type ion implantation apparatus used in the ion implantation method according to one embodiment of the present invention.
FIG. 6 is a graph showing the fluorine concentration of the intraoral device made of stainless steel of Example 1 ion-implanted by the ion implantation method of the present invention.
FIG. 7 is a graph showing the bacterial adhesion amount of the intraoral device made of stainless steel manufactured in Example 1.
FIG. 8 is a graph showing the fluorine concentration of the titanium intraoral device of Example 2 ion-implanted by the ion implantation method of the present invention.
FIG. 9 is a graph showing the fluorine concentration of an intraoral device made of a synthetic resin of Example 3 ion-implanted by the ion implantation method of the present invention.
FIG. 10 is a schematic view showing a state where ions are implanted into an intraoral device of an insulating material.
FIG. 11 is a schematic view showing a state in which a conductive material is provided outside an intraoral device and ion implantation is performed.
FIG. 12 is a graph showing the fluorine concentration of a synthetic resin intraoral device ion-implanted with the PBII device shown in FIG. 11;
FIG. 13 is a graph showing the fluorine concentration of the intraoral device made of silicon rubber of Example 5 ion-implanted by the ion implantation method of the present invention.
FIG. 14 is a graph showing the fluorine concentration of an intraoral device made of silicon rubber which has been ion-implanted with the PBII device shown in FIG. 11;
FIG. 15 is a schematic view showing a method of implanting ions into materials having different aspect ratios.
FIG. 16 is a schematic view showing another example of the plasma type ion implantation apparatus.
[Explanation of symbols]
1. Intraoral device
2. Insulating insulator
3. Vacuum chamber
4: High voltage power supply
5 ... Feedthrough
6 ... Holder
7 Conductive material
8 Plasma source
9 ... Pulse arc power supply
10 ... denture
11 ... artificial teeth
12 ... denture base
13. Occlusal guidance device
14. Orthodontic appliance
15 Exhaust device
16 Plasma source
17 ... Gas supply device
18 ... Control device
19 ... Maintenance device
20 ... denture base
21 ... artificial root
22 ... Alveolar bone
23 ... gingiva
24 ... Sample holder
25 ... Sample
26 ... Shielding plate
27 ... Superstructure

Claims (10)

An intraoral device made by ion-implanting fluorine into part or all of the surface. The part where fluorine is ion-implanted is one of the surface of an artificial tooth, the surface of a denture base, the surface of a maintenance device, the surface of an occlusal guidance device, the surface of an orthodontic appliance, or the surface of a superstructure placed over an artificial dental root An intraoral device according to claim 1. An intraoral device made of metal or porcelain, wherein an antibacterial metal having an antibacterial effect is ion-implanted into a part or the entire surface of the metal or porcelain. The antibacterial metal is ion-implanted into one of a surface of an artificial tooth, a surface of a denture base, a surface of a maintenance device, a surface of an occlusal guidance device, a surface of an orthodontic appliance, and a surface of a superstructure placed over an artificial tooth root. 3. The oral device according to item 3. The oral device according to claim 3, wherein the antimicrobial metal comprises at least one of titanium, silver, copper, and zinc. A conductive material that is conductive and has a gap for the passage of ions is placed outside the intraoral device, and the conductive material is electrically connected to the holder on which the intraoral device is set. And applying a pulsed high voltage to the intraoral device to ion-implant the antimicrobial material from the surface. 7. The method according to claim 6, wherein the antibacterial material is fluorine or an antibacterial metal or both. 7. The method for ion implantation into an intraoral device according to claim 6, wherein one or both of fluorine and an antibacterial metal are ion-implanted by a plasma-based ion implantation technique. 7. The method according to claim 6, wherein the conductive material is a metal net. The method according to claim 9, wherein the conductive material is made of titanium.

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