JP4067071B2 - Dental mucosa conditioning material - Google Patents

Description

【００５０】
（ただし、Ｐｈはフェニル基を示す。）
で示されるオルガノポリシロキサン等が挙げられる。なお、上記化合物及び後述する実施例、比較例に用いられる化合物中の各繰り返し構成単位の結合順序は全く任意であり、構造式中に示される繰り返し構成単位の数は各構成単位の総量を示すにすぎない。
【００５１】
本発明の製造方法で使用する成分（Ｂ）は、ケイ素原子に結合している水素原子を分子中に少なくとも３個有するオルガノハイドロジェンポリシロキサンであり、末端に上記成分（Ａ）の不飽和結合含有シロキサンを架橋させてゴム弾性体とする働きを持つ成分である。
【００５２】
不飽和結合含有シロキサンと反応して架橋構造となるためには、ケイ素原子に結合している水素原子（すなわち、ＳｉＨ基）が分子中に少なくとも３個は必要である。分子中に存在するＳｉＨ基の数が３個より少ないと架橋構造とならずゴム弾性体を得ることができない。
【００５３】
成分（Ｂ）中のＳｉＨシロキサン分子中に存在する有機基は、特に限定されず、たとえば前述した成分（Ａ）の不飽和結合含有シロキサンの分子中に存在する“末端に不飽和結合を有する有機基”以外の有機基と同様のものが例示されるが、合成、入手が容易で且つ硬化後に良好な物理的性質を与えるという点から、メチル基が最も好ましい。かかるＳｉＨシロキサンは、直鎖状、分枝状または環状のいずれであってもよく、これらの混合物であってもよい。
【００５４】
本発明で使用できる成分（Ｂ）の代表的なものを具体的に示せば、
【００５５】
【化２】

【００５６】
また、前記製造方法において、成分（Ａ）及び成分（Ｂ）と共存して反応させてもよい成分（Ｆ）は、ケイ素原子に結合している水素原子を分子中に２個あるいは１個しか含まないオルガノハイドロジェンポリシロキサンである。該成分（Ｆ）を配合すると、弾性率が小さくなる傾向があり、硬化体の粘弾性を調節しやすくなる。
【００５７】
本発明で使用できる成分（Ｆ）の代表的なものを具体的に示せば、
【００５８】
【化３】

で示されるオルガノハイドロジェンポリシロキサン等が挙げられる。上記化合物及び後述する実施例、比較例に用いられる成分（Ｆ）のＳｉＨシロキサンにおいても、成分（Ａ）の不飽和結合含有シロキサンと同様に分子内の各繰り返し構成単位の結合順序は全く任意であり、構造式中に示される繰り返し構成単位の数は各構成単位の総量を示すにすぎない。
【００５９】
前記製造方法において、反応させる成分（Ａ）、成分（Ｂ）、及び必要に応じて添加する成分（Ｆ）の量比は、特に限定されないが、次のような量比とすることにより、前記したような歯科用粘膜調整材として好適な粘弾性を有する硬化体を得ることができる。
【００６０】
即ち、成分（Ｆ）を併用しない場合においては、反応させる成分（Ａ）と成分（Ｂ）との量比は、成分（Ａ）の不飽和結合の総数｛［Ｃ＝Ｃ］_A｝に対する成分（Ｂ）中のケイ素原子に結合している水素原子の総数｛［ＳｉＨ］_B｝の比｛［ＳｉＨ］_B／［Ｃ＝Ｃ］_A｝で表して、０．５〜１．５、特に０．７〜１．５となる量比であることが好適である。
【００６１】
また、成分（Ｆ）を共存させる場合においては、反応させる成分（Ａ）、成分（Ｂ）、及び成分（Ｆ）の量比は、成分（Ａ）の不飽和結合の総数｛［Ｃ＝Ｃ］_A｝に対する成分（Ｂ）中のケイ素原子に結合している水素原子の総数｛［ＳｉＨ］_B｝と成分（Ｆ）中のケイ素原子に結合している水素原子の総数｛［ＳｉＨ］_F｝との和の比｛（［ＳｉＨ］_B＋［ＳｉＨ］_F）／［Ｃ＝Ｃ］_A｝及び［ＳｉＨ］_Bと［ＳｉＨ］_Fの比｛［ＳｉＨ］_B／［ＳｉＨ］_F｝で表して、（［ＳｉＨ］_B＋［ＳｉＨ］_F）／［Ｃ＝Ｃ］_Aが０．５〜５であり、且つ［ＳｉＨ］_B／［ＳｉＨ］_Fが０．５〜１０となる量比、特に［ＳｉＨ］_B＋［ＳｉＨ］_F）／［Ｃ＝Ｃ］_Aが１．０〜３．０であり、且つ［ＳｉＨ］_B／［ＳｉＨ］_Fが０．８〜５．０となる量比であるのが好適である。
【００６２】
本発明の製造方法に使用される成分（Ｃ）は、シリカ系充填剤であり、シリコーンゴムの補強用充填剤として作用する。一般に、シリカ系充填剤を配合することによる補強効果は、分子間力の小さいシリコーンゴムマトリックスにこれらシリカ系充填剤を配合することにより該充填剤の表面付近に水素結合等が生じ、一部結晶化したような構造となるためであると言われている。
【００６３】
成分（C）としては、シリコーンゴムの説明で前記したシリカ系充填剤が制限なく使用できる。
【００６４】
該成分（Ｃ）の配合量は、補強用充填剤としての硬化が充分に発揮できる量であれば特に制限されないが、補強効果および硬化前のペーストの操作性の観点から、成分（Ａ）１００重量部に対して１〜３００重量部が好ましく、また１〜１００重量部がより好ましい。
【００６５】
本発明の製造方法に使用される成分（Ｄ）のヒドロシリル化反応触媒は、前記成分（Ａ）と、成分（B）及び更に必要に応じて添加される成分（Ｆ）とを反応（具体的にはヒドロシリル化反応）させて、オルガノポリシロキサンの架橋体からなるマトリックスを形成するための触媒として作用するものである。成分（Ｄ）は、この様な触媒作用を有するものであれば、通常ヒドロシリル化反応触媒として使用されるものが制限なく使用できる。
【００６６】
好適に使用できる成分（Ｄ）を例示すれば、塩化白金酸、そのアルコール変性物、白金のビニルシロキサン錯体等の白金系触媒、また同様のロジウム系触媒などを挙げることができる。これらの中でも入手の容易さ等の点から白金系触媒が好ましい。なお、保存性を高めるためには、白金のビニルシロキサン錯体のようなクロル分の少ないものを使用するのが好適である。
【００６７】
該成分（Ｄ）の配合量は、ヒドロシリル化反応を充分に進行させる量であれば特に制限されない。一般に、ある程度まではヒドロシリル化反応の速度は成分（Ｄ）の配合量の増加に伴い速くなるが、過剰量の使用は配合量に見合った効果が得られず、経済的に不利になるばかりでなく、逆に架橋反応の制御が難しくなったり、着色等の問題を引き起こす傾向がある。従って、成分（Ｄ）の配合量を決定するに当たっては、この様な点を考慮しつつ各系毎に適宜決定すればよい。因みに、成分（Ｄ）が白金系触媒の場合には、成分（Ｄ）の好適な配合量は、白金黒量として成分（Ａ）及び成分（Ｂ）の合計量に対して０．１〜１０００ｐｐｍの範囲である
また、前記の製造方法においては、必要に応じてヒドロシリル化反応性を有さないオルガノポリシロキサンからなる成分（Ｅ）を配合した後に架橋反応を行っても良い。該成分（Ｅ）は可塑剤として作用するので、架橋反応を成分（Ｅ）の存在下に行うことによって硬化体に更に好適な粘弾性を付与することができる。
【００６８】
成分（Ｅ）のヒドロシリル化反応性を有さないオルガノポリシロキサンとは、分子中に不飽和結合を有する有機基及びケイ素原子に結合している水素原子のどちらも存在しないオルガノポリシロキサンの意味である。
【００６９】
該オルガノポリシロキサン中に存在する有機基としては、成分（Ａ）の不飽和結合含有シロキサンの分子中に存在する“末端に不飽和結合を有する有機基”以外の有機基と同様なものが例示される。即ち、成分（Ｅ）として好適に使用できるオルガノポリシロキサンとしてはジメチルポリシロキサン、メチルフェニルポリシロキサン、及びこれらの共重合体等が挙げられる。これらの中でも、合成、入手が容易で且つ硬化後に良好な物理的性質を与えるという点から、ジメチルポリシロキサンが最も好ましい。
【００７０】
なお、後述する実施例、比較例に用いられる成分（Ｅ）のヒドロシリル化反応性を有さないオルガノポリシロキサンにおいても、成分（Ａ）の不飽和結合含有シロキサン、成分（Ｂ）のＳｉＨシロキサンと同様に分子内の各繰り返し構成単位の結合順序は全く任意であり、構造式中に示される繰り返し構成単位の数は各構成単位の総量を示すにすぎない。
【００７１】
また該成分（Ｅ）のヒドロシリル化反応性を有さないオルガノポリシロキサンの粘度は特に限定されないが、硬化体から溶出し難く硬化体がべた付かないという観点から、より高粘度、すなわち高分子量のものが好ましい。具体的には１０ポイズ以上の粘度を有するもの、特に１０００ポイズ以上の粘度を有するものがより好ましい。
【００７２】
成分（Ｅ）の配合量は、適度な粘弾性を付与する効果、及び硬化体のベタツキ防止等の観点から、成分（Ａ）１００重量部に対して１〜１００重量部となるような量とすることが好ましい。
【００７３】
また、前記した各種添加剤を配合する場合には、架橋反応を行う前にこれら各成分を配合すればよい。
【００７４】
前記の製造方法においては、通常、成分（Ｂ）及び／又は成分（Ｆ）と成分（Ｄ）が共存しない形態（保存中にヒドロシリル化反応が起こらない形態）、例えば、成分（Ａ）、成分（Ｂ）、成分（Ｃ）並びに必要に応じて成分（Ｆ）、成分（Ｅ）、及び各種添加剤を含む甲剤と、成分（Ａ）、成分（Ｃ）、成分（Ｄ）並びに必要に応じて成分（Ｅ）、及び各種添加剤を含む乙剤とからなる２ペースト型、あるいはペースト＋液型等のキットとして調整され、使用直前に両者を混合して反応を行い架橋させるのが一般的である。
【００７５】
なお、本発明の歯科用粘膜調整材を製造するにあたって、施術者には上記のキットが提供されるため、場合によっては該キット、又は該キットを構成する２種類の組成物（更には両組成物を混合して得られる組成物）が歯科用粘膜調整材と呼ばれることもあるが、本明細書ではこれらをそれぞれ歯科用粘膜調整材用キット、又は歯科用粘膜調整材用組成物と称し、反応後に得られる硬化体を歯科用粘膜調整材と称する。
【００７６】
前記の製造方法において好適に使用できる歯科用粘膜調整材用キットとしては、 下記（Ｉ）及び（II）のようなものが挙げられる。
【００７７】
（Ｉ） 下記条件（１）、（２）、及び（３）を満足する２種類の歯科用粘膜調整材用組成物１（ＣＯＭＰ−１）及び歯科用粘膜調整材用組成物２（ＣＯＭＰ−２）の組み合わせからなることを特徴とする歯科用粘膜調整材用キット。
（１） 前記ＣＯＭＰ−１及び前記ＣＯＭＰ−２は、成分（Ａ）、成分（Ｂ）、成分（Ｃ）、及び成分（Ｄ）から選ばれる少なくとも１つの成分を含む。
（２） 前記ＣＯＭＰ−１とＣＯＭＰ−２との組み合わせには、前記成分（Ａ）乃至成分（Ｄ）の全ての成分が含まれ、該組み合わせ中の各成分の量比は、
成分（Ａ）：１００重量部、
成分（Ｂ）：成分（Ａ）の不飽和結合の総数｛［Ｃ＝Ｃ］_A｝に対する成分（Ｂ）中のケイ素原子に結合している水素原子の総数｛［ＳｉＨ］_B｝の比｛［ＳｉＨ］_B／［Ｃ＝Ｃ］_A｝で表して、０．５〜１．５となる量、
成分（Ｃ）：１〜３００重量部、及び
成分（Ｄ）：触媒量
である。
（３） 前記ＣＯＭＰ−１又は前記ＣＯＭＰ−２のいずれにおいても成分（Ｂ）と成分（Ｄ）とは共存しない。
【００７８】
（II） 下記条件（１）、（２）、及び（３）を満足する２種類の歯科用粘膜調整材用組成物３（ＣＯＭＰ−３）及び歯科用粘膜調整材用組成物４（ＣＯＭＰ−４）の組み合わせからなることを特徴とする歯科用粘膜調整材用キット。
（１） 前記ＣＯＭＰ−３及び前記ＣＯＭＰ−４は、成分（Ａ）、成分（Ｂ）、成分（Ｆ）、成分（Ｃ）、及び成分（Ｄ）から選ばれる少なくとも１つの成分を含む。
（２） 前記ＣＯＭＰ−３と前記ＣＯＭＰ−４との組み合わせには、前記成分（Ａ）乃至成分（Ｄ）、及び成分（Ｆ）の全ての成分が含まれ、該組み合わせ中の各成分の量比は、
成分（Ａ）：１００重量部、
成分（Ｂ）及び成分（Ｆ）：それぞれ、成分（Ａ）の不飽和結合の総数｛［Ｃ＝Ｃ］_A｝に対する成分（Ｂ）中のケイ素原子に結合している水素原子の総数｛［ＳｉＨ］_B｝と成分（Ｆ）中のケイ素原子に結合している水素原子の総数｛［ＳｉＨ］_F｝との和の比｛（［ＳｉＨ］_B＋［ＳｉＨ］_F）／［Ｃ＝Ｃ］_A｝及び［ＳｉＨ］_Bと［ＳｉＨ］_Fの比｛［ＳｉＨ］_F／［ＳｉＨ］_B｝で表して、（［ＳｉＨ］_B＋［ＳｉＨ］_F）／［Ｃ＝Ｃ］_Aが０．５〜５となり且つ［ＳｉＨ］_F／［ＳｉＨ］_Bが０．５〜１０となる量、
成分（Ｃ）：１〜３００重量部、及び
成分（Ｄ）：触媒量
である。
（３） 前記ＣＯＭＰ−３又は前記ＣＯＭＰ−４のいずれにおいても成分（Ｄ）と成分（Ｂ）及び／又は成分（Ｆ）とは共存しない。
【００７９】
また、上記（Ｉ）の（２）における好適な量比は、［ＳｉＨ］_B／［Ｃ＝Ｃ］_Aが０．７〜１．５となる量比であり、上記（II）の（２）における好適な量比は（［ＳｉＨ］_B＋［ＳｉＨ］_F）／［Ｃ＝Ｃ］_Aが１．０〜３．０となり且つ［ＳｉＨ］_F／［ＳｉＨ］_Bが０．８〜５．０となる量比である。
【００８０】
また、上記の各歯科用粘膜調整材用キットにおいては、それぞれ（１）〜（３）で示される条件を満足しさえすれば、キットを構成する各歯科用粘膜調整材用組成物に、成分（Ｅ）やシリカ系充填剤以外の各種充填剤や各種添加剤を適宜配合してもよい。
【００８１】
歯科用粘膜調整材用キットを構成する各歯科用粘膜調整材用組成物の調製方法は、特に限定されず、成分（Ａ）、成分（Ｂ）、成分（Ｃ）、成分（Ｄ）、成分（Ｅ）、成分（Ｆ）、並びに各種充填剤及び添加剤の中から必要成分を適量計量し、ニーダー、プラネタリー等の一般的な混練機、あるいは一般的な撹拌機によって均一になるまで混練、撹拌する事により、ペースト状あるいは液状の組成物を得ることができる。
【００８２】
本発明の歯科用粘膜調整材を製造するに際しては、使用直前に前記２種類の歯科用粘膜調整材用組成物を所定量計量し、混練後、予め接着剤を塗布した義歯裏面に盛って患者の口腔内に充分に硬化するまで保持し、硬化後口腔内から取り出して余剰部分を取り除けばよい。
【００８３】
なお、上記接着剤としては、特開平７−７０２４６号公報、特開平７−７６６１１号公報等に記載されているシリコーン修飾アクリル系共重合体系の接着剤を用いるのが好適である。
【００８４】
【実施例】
本発明を更に具体的に説明するために実施例を示すが、本発明はこれらの実施例に限定されるものではない。
【００８５】
以下の実施例に使用するオルガノポリシロキサンを表１にまとめて示す。
【００８６】
【表１】

以下の実施例、比較例において、歯科用粘膜調整材の評価は下記の方法によって行い、同一試料について３回測定してその平均値を記録した。
【００８７】
（１）正弦正接（ｔａｎδ）：短冊状の硬化体を作製し、３７℃水中に２時間保存後に、動的粘弾性測定装置を用いて、３７℃、１Ｈｚ、引っ張り負荷の条件で測定を行い、正弦正接を求めた。
【００８８】
（２）弾性歪み：直径１３ｍｍ、高さ２０ｍｍの硬化体を作製し、３７℃水中に２時間保存後、２３℃の室内に５分間静置し、その後、以下の方法に従って弾性歪みを測定した。
【００８９】
まず、１０ｋＰａの荷重を加え、３０秒経過した時の高さを読みとる（Ａ）。更に３０秒後、総荷重が１００ｋＰａとなるように追加荷重を１０秒間かけて乗せ、荷重終了から３０秒後の高さを読みとる（Ｂ）。これらの測定値から以下の式より弾性歪みを算出する。
弾性歪み（％）＝（Ａ−Ｂ）÷２０×１００
（３）永久歪み：直径１３ｍｍ、高さ２０ｍｍの硬化体を作製し、３７℃水中に２時間保存後、２３℃の室内に５分間静置し、その後、以下の方法に従って永久歪みを測定した。
【００９０】
まず、４ｋＰａの荷重を加え、２５秒経過した時の高さを読みとる（Ｃ）。その後、５秒間かけて１２％（２．４ｍｍ）の変形を与え、３０秒間保持する。そして、３０秒間無荷重状態とした後、再び４ｋＰａの荷重をかけ、３０秒後の高さを読みとる（Ｄ）。これらの測定値から、以下の式より永久歪みを算出する。
永久歪み（％）＝（Ｃ−Ｄ）÷２０×１００
（４）ショア硬度：直径９ｍｍ、高さ１２ｍｍの硬化体を作製し、３７℃水中に２時間保存した。その後、２３℃の室内に５分間静置し、スプリング式硬さ試験機（A型）によって９．８Nの荷重を加え、３０秒経過した時の値をショア硬度とした。
【００９１】
（５）着色量：１０ｍｍ×１０ｍｍ×２ｍｍの硬化体を作製し、３７℃水中に２時間保存後、色差計により着色前のＬ^*、ａ^*、ｂ^*を測定する。その後、試験片を５ｗｔ％コーヒー水溶液に浸漬し、攪拌しながら４０℃で２４時間保存する。保存後、水洗、乾燥し、再び色差計でＬ^*、ａ^*、ｂ^*を測定し、それらの差、ΔＬ^*、Δａ^*、Δｂ^*より、次式を用いて着色量（ΔＥ^*）を求める。
着色量（ΔＥ^*）＝｛（ΔＬ^*）²＋（Δａ^*）²＋（Δｂ^*）²｝^1/2
（６）物性の経時安定性：サンプルを３７℃水中に７日間保存した後の弾性歪み、永久歪み及びショア硬度を上記（２）、（３）及び（４）に従って測定する。
【００９２】
（７）義歯床からの除去の容易性の評価：義歯床と同様にして作製されたレジン板に接着剤を塗布した後、接着剤の塗布面に歯科用粘膜調整材を盛りつけ、硬化させた。３７℃水中で１週間保存後、レジン板から歯科用粘膜調整材をナイフ、歯科用回転式研削機等によって剥がした。この時の剥がれ易さを、Ａ：ナイフのみによって簡単に削除可能、Ｂ：一部研削機が必要、Ｃ：研削機によってのみ削除可能、の３段階で評価した。評価は、Ａが優れ、Ｃが劣る。なお、接着剤としては、本発明の歯科用粘膜調整材については下記構造式
【００９３】
【化４】

で示される平均組成を有する共重合体の０．５ｗｔ％塩化メチレン溶液を使用し、アクリル系粘膜調整材については特に何も使用しなかった。
【００９４】
実施例１
表１に示す化合物ａを５０重量部、化合物ｂを５０重量部、白金のビニルシロキサン錯体を化合物ａ、ｂの総量に対して白金が１００ｐｐｍとなるような量、乾式シリカ１５重量部をプラネタリーに入れ、均一になるまで混練し、ペースト甲とした。
【００９５】
表１に示す化合物ａを５０重量部、化合物ｂを５０重量部、化合物ｅを２．０重量部、乾式シリカ１５重量部をプラネタリーに入れ、均一になるまで混練し、ペースト乙とした。
【００９６】
この甲、乙二種類のペーストを混合比１対１で混練し、前述の評価方法に従って評価した。結果を表５に示す。
【００９７】
実施例２〜１２
表２、表３及び表４に示す各組成の材料を実施例１と同様にしてプラネタリーによって混練して、各ペーストを調製した。なお、白金触媒は実施例１で用いたものと同じものを用いた。また、これら表において表面処理乾燥式シリカとは、乾燥式シリカをヘキサメチルジシラザン等のシランカップリング剤により表面処理したものである。
【００９８】
【表２】

【００９９】
【表３】

【０１００】
【表４】

【０１０１】
各ペーストを用いて上記評価方法に従って試験を行った。結果を表５に示す。
【０１０２】
【表５】

比較例１
メタクリル酸エチル１２０重量部、ブチルフタリルグリコール酸ブチル８５重量部、及びエタノール１５重量部からなる組成のアクリル系粘膜調整材を用いて上記評価方法に従って試験を行った。結果を表５に示す。
【０１０３】
比較例２
メタクリル酸ブチル（９０モル％）−メタクリル酸エチル（１０モル％）共重合体１１０重量部、及びブチルフタリルグリコール酸ブチル１００重量部からなる組成を有するアクリル系粘膜調整材を用いて上記評価方法に従って試験を行った。結果を表５に示す。
【０１０４】
比較例３
メタクリル酸ブチル（８０モル％）−メタクリル酸エチル（２０モル％）共重合体１１０重量部、及びフタル酸ジブチル１００重量部からなる組成を有するアクリル系粘膜調整材を用いて上記評価方法に従って試験を行った。結果を表５に示す。
【０１０５】
表５の結果より、本発明の歯科用粘膜調整材（実施例１〜１２）は、使用所期から７日間経過後を通して充分な正弦正接（ｔａｎδ）、弾性歪み、永久歪み、及びショア硬度を保持しており、着色量も少なく、使用後の義歯床からの除去も容易である。これに対してアクリル系粘膜調整材（比較例１〜３）では、初期には充分な正弦正接（ｔａｎδ）、弾性歪み、永久歪み、ショア硬度は有するものの、経時的に各物性が低下している。また、着色量も大きく、使用後の義歯床からの除去も難しい。このことから本発明の歯科用粘膜調整材は、耐久性及び作業性の点で優れていることが分かる。
【０１０６】
【発明の効果】
本発明の歯科用粘膜調整材は、適度な粘弾性特性を長期間に渡って有しており患者に疼痛を与えることなく、炎症治癒に伴って粘膜形状を自然な状態に回復させることが出来る。また、本発明の歯科用粘膜調整材は、生体に刺激を与えるような材料を基本的に使用しておらず、口腔粘膜で使用したときの汚れも少なく、さらに使用後において義歯床から容易に除去できるという、従来の歯科用粘膜調整材には見られない優れた特徴を有する。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a dental mucosa preparation material for a denture wearing patient having deformation or inflammation of the oral mucosa among denture lining materials used in dental treatment.
[0002]
[Prior art]
If the denture is used for a long time, the compatibility with the denture gradually deteriorates due to absorption of the alveolar ridge and the maintenance and stability become poor. If the incompatible denture continues to be used as it is, uneven pressure is applied to the submucosa, causing ulcers and inflammation, and causing pain due to occlusal pressure. For this reason, when such incompatibility occurs, it is necessary to prepare a new denture or to rebase the denture in use to restore the denture to the mucous membrane.
[0003]
However, since the patient's oral mucosa is unstable due to ulcers and inflammation as described above, the preparation and rebasing of new dentures waits for the oral mucosa to be healthy in order to restore good compatibility. It is necessary to do afterwards.
[0004]
The material used in such a case is a dental mucosa adjusting material. The dental mucosa-adjusting agent is used by lining the mucosal surface of the denture in use until the shape and color of the submucosa in the denture base are restored to normal.
[0005]
Currently, there are three types of soft materials related to the denture base: denture base fixing glue (so-called denture stabilizing material), dental mucosa adjusting material, and soft lining material. The purpose of use, method, period of use, and required properties are also different.
[0006]
For example, the denture base fixing adhesive is used for a short period of time, which is one to several days after the person himself performs the treatment. Therefore, as the paste material for fixing the denture base, a material that does not completely adhere to the denture base but develops an adhesive strength of an adhesive level is required. On the other hand, both the dental mucosa adjusting material and the soft lining material are common in that the practitioner is a doctor, but the required physical properties are greatly different depending on the purpose of use. Specifically, as described above, the dental mucosa conditioning material is used for the treatment of the oral mucosa in the previous stage of denture repair, and it must be flexible and capable of plastic deformation for that purpose. The period of use is also a relatively short period (1 week to several weeks) until the oral mucosa is restored to a healthy state. On the other hand, since the soft lining material is a material for repairing the denture, it is required not to be deformed for a long time after the repair.
[0007]
As described above, all of the above three types of materials are soft materials that are used with dentures lined (backed), but their classification is clearly different as dental materials because of their intended use and required performance. It is to make.
[0008]
At present, as a dental mucosa preparation material, a kneading material of a liquid component comprising a powder component comprising polyethyl methacrylate or a copolymer thereof and a phthalate ester plasticizer containing about 4 to 20% by weight of ethanol is generally used. Is used. The mucous membrane adjusting material becomes a soft elastic body when the powder component and the liquid component are mixed, so when this material is lined on the mucosal surface of the incompatible denture, the compatibility of the denture is restored and pain due to occlusal pressure is reduced. Can be relaxed. In addition, when the pain is alleviated, the ulcers and inflammation of the oral mucosa disappear and the form of the oral mucosa is restored to the original state over time. It has an excellent feature that it deforms in accordance with changes in the shape of the mucous membrane.
[0009]
[Problems to be solved by the invention]
However, the above-mentioned dental mucosa preparation material has problems in the following points (1) to (3).
[0010]
That is, (1) The problem that the plasticizer and ethanol are eluted during use, which becomes harder over time, is concerned about the influence on the living body, has an unpleasant taste, or receives irritation. , (2) The problem that the oil and saliva, etc. in the food are absorbed during the period of use and it becomes dirty and bad odor is generated, and (3) The dental treatment used for the lining material treatment after the treatment is finished It is necessary to remove the mucosa preparation material from the denture base, but since the dental mucosa preparation material is composed of a material that is basically the same quality as the denture base, it is difficult to control the adhesive force. There is a problem that it is very difficult to remove (specifically, grind) the mucosa-adjusting material adhered firmly.
[0011]
An object of the present invention is to develop a dental mucosa-adjusting material that does not have the above problems (1) to (3).
[0012]
[Means for solving problems]
As a result of intensive studies to solve the above-mentioned problems, the present inventors have used silicone rubber, particularly room temperature addition polymerization type silicone rubber, which has not been used in conventional dental mucosa preparation materials, and the above (1) to (3). The present inventors have succeeded in obtaining a dental mucosa-adjusting material having no problems as described above, and have completed the present invention.
[0013]
  That is,BookThe invention relates to an organopolysiloxane {component (A)} having at least two organic groups having an unsaturated bond at the end thereof and an organohydrosiloxane having at least three hydrogen atoms bonded to silicon atoms in the molecule. A dental mucosa-adjusting material characterized by reacting Genpolysiloxane {component (B)} with a hydrosilylation catalyst {component (D)} in the presence of a silica-based filler {component (C)} It is a manufacturing method.
[0014]
Silicone rubber is a material having excellent characteristics as a dental material that is water-repellent, non-adhesive, and physiologically non-toxic. However, a dental mucosa-adjusting material consisting essentially of silicone rubber has been known so far. Absent.
[0015]
  Of the present inventionObtained by manufacturing methodThe dental mucosa preparation material is essentially composed of a silicone rubber consisting essentially of colorless, tasteless, odorless, non-volatile, and non-toxic components.Of the previous twoThere is no problem. In addition, since it is possible to design an adhesive that controls the adhesive force with a resin that is a denture base,ThirdThe problem can be solved.
[0016]
  The present inventionManufactured byIn the dental mucosa conditioning material,the abovesilicone rubberIsIt is a room temperature addition polymerization type silicone rubberBecause, The molding can be performed directly in the oral cavity.
[0017]
Further, the mucosa preparation material of the present invention is such that the silicone rubber used is (i) an elastic strain of 15% or more, preferably 20% or more, and its permanent strain is 0.5% or more. (Ii) When the sine tangent is 0.5 or more, or (iii) when the Shore hardness is 15 or less, the plasticity is appropriately plastically deformed as the damaged mucous membrane heals, while maintaining appropriate elasticity. Excellent performance as a mucosa-adjusting material.
[0018]
Such physical properties can be realized by adjusting the crosslinking density of the silicone rubber, the amount of silica-based filler and other fillers that serve as a reinforcing material, and the blending amount of organopolysiloxane as a plasticizer.
[0019]
  In the present invention, a dental mucosa-adjusting material comprising a room temperature addition polymerization type silicone rubber suitable for the above reasons is obtained by the production method..
[0020]
The above method is basically a method for producing silicone rubber by so-called room temperature addition polymerization, but not only can the silicone rubber be molded into a desired shape as a dental mucosa preparation material in the oral cavity of a patient, but also harmful. Therefore, it can be said that it is an excellent method for producing a dental mucosa preparation material.
[0021]
DETAILED DESCRIPTION OF THE INVENTION
  Of the present inventionObtained by manufacturing methodDental mucosal conditioner isThe specific filler described later, wherein the filler is a silica-based filler.Made of ricone rubber.
[0022]
Here, the silicone rubber means a viscoelastic body in which fillers and various additives are substantially uniformly dispersed in a matrix composed of a crosslinked organopolysiloxane.
[0023]
  Above fillerSpecific examples of silica-based fillersFor example, ground quartz, fused silica powder, wet silica powder, dry silica powderEtc.can give.
[0024]
  theseSilica-based fillerWorks as a reinforcing material for the above matrix.TheAlmost essential component is added. This also applies to the silicone rubber used in the present invention.
[0025]
In addition, the above various additives specifically include hydrogen gas absorbents such as black platinum or fine palladium; reaction inhibitors such as 1,3-divinyltetramethyldisiloxane; 2,4-dihydroxybenzophenone UV absorbers; pigments such as titanium dioxide; antioxidants such as BHT; antibacterial agents such as chitosan; plasticizers such as silicone oil;
[0026]
Various fillers and various additives other than the silica-based filler described above are appropriately added depending on the purpose.
[0029]
  The silicone rubber used in the method of the present invention can be polymerized and cured into a desired shape in the oral cavity, has no by-products during the curing reaction, and has excellent durability during use in the oral cavity. -Rubber has been adopted.
[0030]
The silicone rubber used in the present invention has an elastic strain of 15% or more, preferably 20% or more and a permanent strain of 0.5% or more, or a sine tangent of 0.5 or more. Or its Shore hardness is preferably 15 or less.
[0031]
Here, the elastic strain and the permanent strain were measured according to JIS T6513-1991 using a sample prepared according to the sample preparation conditions of ISO 10139-1 (Dentistry-Resilient lining materials for removable dentures-Part 1: Short-term materials). It is a value measured by a dental rubber elastic impression material).
[0032]
Further, the sine tangent (tan δ) is a value measured by a dynamic viscoelasticity measuring apparatus using a sample prepared in the same manner as described above at 37 ° C. and 1 Hz under the conditions of tension addition.
[0033]
Further, the Shore hardness is a value measured by JIS K6301-1975 (spring type hardness test) using a sample prepared in the same manner as described above.
[0034]
When the elastic strain of the silicone rubber used in the present invention is 15% or more, preferably 20% or more, the permanent set is 0.5% or more, the sine tangent is 0.5 or more, and the Shore hardness is 15 or less In particular, when the silicone rubber is used as a mucosa-adjusting material, it does not give pain to the patient, and it is particularly excellent in the property of being deformed according to the shape of the mucosa so as not to inhibit the recovery of the mucosa. Yes.
[0035]
The more preferable elastic strain of the silicone rubber used in the present invention is 25% or more, and the permanent strain is 0.7% or more. Moreover, the more preferable sine tangent of the silicone rubber used in the present invention is 0.7 or more. Further, the more preferred Shore hardness of the silicone rubber used in the present invention is 12 or less.
[0036]
  In the present invention,In order to use the silicone rubber having such properties as a dental mucosa-adjusting material, the following production method is carried out.
[0037]
  That is, an organopolysiloxane {component (A)} having at least two organic groups having an unsaturated bond at the end thereof and an organohydrogen having at least three hydrogen atoms bonded to silicon atoms in the molecule. In this method, polysiloxane {component (B)} is reacted with hydrosilylation catalyst {component (D)} in the presence of silica-based filler {component (C)}.
[0038]
In addition, when the said reaction is performed in a patient's oral cavity, the said method becomes the manufacturing method of the dental mucosa adjustment material of this invention as it is.
[0039]
In the above production method, the reaction may be carried out in the presence of an organohydrogenpolysiloxane {component (F)} having two or one hydrogen atom bonded to a silicon atom in the molecule.
[0040]
The component (B) serves as a crosslinking agent for crosslinking the component (A), and the component (D) serves as a catalyst for a hydrosilylation reaction that is a crosslinking reaction. In addition, the component (C) functions as a reinforcing material that imparts mechanical strength to the silicone rubber.
[0041]
In the above production method, the crosslinking density is adjusted by controlling the ratio of the component (B) to the component (A), and the flexibility and plastic deformability (elastic strain, permanent strain, sine tangent) of the resulting silicone rubber are adjusted. , Physical properties such as Shore hardness) can be adjusted. Such preparation is sufficiently possible only by controlling the amount ratio of the component (A) to the component (B). However, when the reaction is performed in combination with the component (F), the control is further facilitated. Become.
[0042]
  toothSubstantial physical properties of medical mucous membrane conditioners are determined by the silicone rubber usedBy the way, The above manufacturing methodThenViscoelasticity suitable as a dental mucosa adjusting material can be realized by controlling the amount ratio of the component (A) and the component (B) and the component (F) as necessary. The viscoelasticity suitable as a dental mucosa adjusting material here is that it has a suitable balance of moderate elasticity for alleviating pain and moderate viscosity (fluidity) following the deformation of the mucous membrane at the same time. The above-mentioned elastic strain, permanent strain, sine tangent, Shore hardness, and preferred ranges thereof have been proposed by the present inventors for the first time as possible indications for such viscoelasticity as a dental mucosal conditioner. It is.
[0043]
Hereinafter, the manufacturing method will be described in detail. For convenience of explanation, hereinafter, “organopolysiloxane having an unsaturated bond in the molecule” and “organohydrogenpolysiloxane having hydrogen bonded to a silicon atom (corresponding to SiH group) in the molecule” "Is also simply referred to as" unsaturated bond-containing siloxane "and" SiH siloxane ", respectively.
[0044]
The component (A) used in the production method is not limited as long as it is an organopolysiloxane having at least two organic groups having an unsaturated bond at its end in one molecule. It may be branched or a mixture thereof.
[0045]
The viscosity is not particularly limited, but is preferably about 10 to 10,000 poise from the viewpoint of the properties of the paste before curing and the properties of the cured product obtained after curing. A more preferred viscosity is about 10 to 3000 poise. However, the said viscosity means the viscosity of a mixture, when mixing and using several types of unsaturated bond containing siloxane as a component (A).
[0046]
Examples of the organic group having an unsaturated bond at the terminal existing in the molecule of the unsaturated bond-containing siloxane of component (A) include vinyl group, allyl group, 1-butenyl group, ethynyl group, etc. A vinyl group is most preferred because of its availability. These organic groups having an unsaturated bond at the end may exist at the end of the molecular chain of the organosiloxane, at the middle of the molecular chain, or both, but the reactivity at the time of curing, after the curing It is preferable that at least one is present at the terminal in order for the cured product of the above to have excellent physical properties.
[0047]
Examples of the organic group other than the above-mentioned “organic group having an unsaturated bond at the terminal” present in the unsaturated bond-containing siloxane molecule of component (A) include a methyl group, an ethyl group, a propyl group, a butyl group, and an octyl group. Examples thereof include alkyl groups such as phenyl groups, aryl groups such as phenyl groups, substituted alkyl groups such as chloromethyl groups and 3,3,3-trifluoropropyl groups, etc. Methyl groups are most preferred because they give good physical properties after curing.
[0048]
If a typical thing of the component (A) which can be used by this invention is shown concretely,
[0049]
[Chemical 1]

[0050]
(However, Ph represents a phenyl group.)
The organopolysiloxane shown by these is mentioned. In addition, the order of bonding of each repeating structural unit in the above-mentioned compounds and the compounds used in Examples and Comparative Examples described later is completely arbitrary, and the number of repeating structural units shown in the structural formula indicates the total amount of each structural unit. Only.
[0051]
The component (B) used in the production method of the present invention is an organohydrogenpolysiloxane having at least three hydrogen atoms bonded to silicon atoms in the molecule, and the unsaturated bond of the component (A) is terminated at the terminal. It is a component that has a function of crosslinking the siloxane to form a rubber elastic body.
[0052]
In order to react with the unsaturated bond-containing siloxane to form a crosslinked structure, at least three hydrogen atoms bonded to silicon atoms (that is, SiH groups) are required in the molecule. If the number of SiH groups present in the molecule is less than 3, a crosslinked structure cannot be obtained and a rubber elastic body cannot be obtained.
[0053]
The organic group present in the SiH siloxane molecule in the component (B) is not particularly limited. For example, the “organic having an unsaturated bond at the terminal” present in the unsaturated bond-containing siloxane molecule of the component (A) described above. Examples of the organic group other than the “group” are exemplified, but a methyl group is most preferable because it is easy to synthesize and obtain and gives good physical properties after curing. Such SiH siloxane may be linear, branched or cyclic, or a mixture thereof.
[0054]
If the typical thing of the component (B) which can be used by this invention is shown concretely,
[0055]
[Chemical formula 2]

[0056]
In the above production method, the component (F) that may be allowed to react with the component (A) and the component (B) has only two or one hydrogen atom bonded to the silicon atom in the molecule. It is an organohydrogenpolysiloxane that does not contain. When this component (F) is mix | blended, there exists a tendency for an elasticity modulus to become small, and it becomes easy to adjust the viscoelasticity of a hardening body.
[0057]
If the typical thing of the component (F) which can be used by this invention is shown concretely,
[0058]
[Chemical Formula 3]

The organohydrogenpolysiloxane shown by these is mentioned. In the SiH siloxane of the component (F) used in the above-mentioned compounds and the examples and comparative examples described later, the bonding order of each repeating structural unit in the molecule is completely arbitrary as in the unsaturated bond-containing siloxane of the component (A). Yes, the number of repeating structural units shown in the structural formula only indicates the total amount of each structural unit.
[0059]
In the production method, the amount ratio of the component (A) to be reacted, the component (B), and the component (F) to be added as necessary is not particularly limited. A cured product having viscoelasticity suitable as such a dental mucosa-adjusting material can be obtained.
[0060]
That is, when the component (F) is not used in combination, the amount ratio of the component (A) to the component (B) to be reacted is the total number of unsaturated bonds {[C = C]_A} The total number of hydrogen atoms bonded to the silicon atom in component (B) for {{SiH]_B} Ratio {[SiH]_B/ [C = C]_A}, It is preferable that the quantity ratio is 0.5 to 1.5, particularly 0.7 to 1.5.
[0061]
When the component (F) is allowed to coexist, the amount ratio of the component (A), the component (B), and the component (F) to be reacted is the total number of unsaturated bonds of the component (A) {[C = C ]_A} The total number of hydrogen atoms bonded to the silicon atom in component (B) for {{SiH]_B} And the total number of hydrogen atoms bonded to silicon atoms in component (F) {[SiH]_F} To the sum ratio {([SiH]_B+ [SiH]_F) / [C = C]_A} And [SiH]_BAnd [SiH]_FRatio {[SiH]_B/ [SiH]_F} And ([SiH]_B+ [SiH]_F) / [C = C]_A0.5 to 5 and [SiH]_B/ [SiH]_FIs a quantity ratio of 0.5 to 10, especially [SiH]_B+ [SiH]_F) / [C = C]_A1.0-3.0 and [SiH]_B/ [SiH]_FIt is preferable that the amount ratio is 0.8 to 5.0.
[0062]
Component (C) used in the production method of the present invention is a silica-based filler, which acts as a reinforcing filler for silicone rubber. In general, the reinforcing effect obtained by blending silica-based fillers is that, by blending these silica-based fillers in a silicone rubber matrix having a small intermolecular force, hydrogen bonds and the like are generated near the surface of the fillers, resulting in partial crystals. It is said that it is because it becomes a structure like that.
[0063]
As the component (C), the silica-based filler described in the description of the silicone rubber can be used without limitation.
[0064]
The amount of the component (C) is not particularly limited as long as it can be sufficiently cured as a reinforcing filler, but from the viewpoint of the reinforcing effect and the operability of the paste before curing, the component (A) 100 The amount is preferably 1 to 300 parts by weight, more preferably 1 to 100 parts by weight with respect to parts by weight.
[0065]
The component (D) hydrosilylation reaction catalyst used in the production method of the present invention reacts the component (A) with the component (B) and the component (F) added as necessary (specifically). And hydrosilylation reaction) to act as a catalyst for forming a matrix composed of a crosslinked organopolysiloxane. As the component (D), those usually used as hydrosilylation reaction catalysts can be used without limitation as long as they have such a catalytic action.
[0066]
Examples of the component (D) that can be suitably used include chloroplatinic acid, alcohol-modified products thereof, platinum-based catalysts such as platinum vinylsiloxane complexes, and similar rhodium-based catalysts. Among these, platinum-based catalysts are preferable from the viewpoint of availability. In order to improve the storage stability, it is preferable to use a material having a low chloro content such as a platinum-vinylsiloxane complex.
[0067]
The blending amount of the component (D) is not particularly limited as long as the amount allows the hydrosilylation reaction to proceed sufficiently. Generally, the hydrosilylation reaction speed increases to some extent with the increase in the amount of component (D). However, the use of an excessive amount does not provide an effect commensurate with the amount, and is not only economically disadvantageous. On the other hand, it tends to be difficult to control the crosslinking reaction or cause problems such as coloring. Therefore, when determining the blending amount of the component (D), it may be appropriately determined for each system in consideration of such points. Incidentally, when the component (D) is a platinum-based catalyst, the preferred blending amount of the component (D) is 0.1 to 1000 ppm with respect to the total amount of the component (A) and the component (B) as the platinum black amount. Is in the range
Moreover, in the said manufacturing method, you may perform a crosslinking reaction, after mix | blending the component (E) which consists of organopolysiloxane which does not have hydrosilylation reactivity as needed. Since this component (E) acts as a plasticizer, a more suitable viscoelasticity can be imparted to the cured product by carrying out a crosslinking reaction in the presence of the component (E).
[0068]
The organopolysiloxane having no hydrosilylation reactivity of component (E) means an organopolysiloxane in which neither an organic group having an unsaturated bond nor a hydrogen atom bonded to a silicon atom exists in the molecule. is there.
[0069]
Examples of the organic group present in the organopolysiloxane include those similar to the organic groups other than the “organic group having an unsaturated bond at the terminal” present in the unsaturated bond-containing siloxane molecule of component (A). Is done. That is, examples of the organopolysiloxane that can be suitably used as the component (E) include dimethylpolysiloxane, methylphenylpolysiloxane, and copolymers thereof. Of these, dimethylpolysiloxane is most preferred because it is easy to synthesize and obtain and gives good physical properties after curing.
[0070]
In addition, in the organopolysiloxane having no hydrosilylation reactivity of the component (E) used in Examples and Comparative Examples described later, the unsaturated bond-containing siloxane of the component (A), the SiH siloxane of the component (B) Similarly, the order of bonding of each repeating structural unit in the molecule is completely arbitrary, and the number of repeating structural units shown in the structural formula only indicates the total amount of each structural unit.
[0071]
In addition, the viscosity of the organopolysiloxane having no hydrosilylation reactivity of the component (E) is not particularly limited, but from the viewpoint of being hard to elute from the cured product and not sticking to the cured product, a higher viscosity, that is, a higher molecular weight. Those are preferred. Specifically, those having a viscosity of 10 poise or more, particularly those having a viscosity of 1000 poise or more are more preferable.
[0072]
The amount of component (E) is 1-100 parts by weight with respect to 100 parts by weight of component (A) from the viewpoint of imparting appropriate viscoelasticity and prevention of stickiness of the cured product, and the like. It is preferable to do.
[0073]
Moreover, what is necessary is just to mix | blend each of these components, before performing a crosslinking reaction, when mix | blending the above-mentioned various additives.
[0074]
In the above production method, the component (B) and / or the component (F) and the component (D) are usually not present (a form in which hydrosilylation reaction does not occur during storage), for example, the component (A), the component (B), component (C) and, if necessary, component (F), component (E), and an additive containing various additives, component (A), component (C), component (D) and necessary It is generally prepared as a two-paste type or paste + liquid type kit consisting of component (E) and an additive containing various additives, mixed and reacted immediately before use for crosslinking. Is.
[0075]
In producing the dental mucosa preparation material of the present invention, the above-mentioned kit is provided to the practitioner, so that in some cases, the kit or two types of compositions constituting the kit (and both compositions) The composition obtained by mixing the product) is sometimes referred to as a dental mucosa adjusting material, but in the present specification, these are respectively referred to as a dental mucosa adjusting material kit or a dental mucosal adjusting material composition, The cured product obtained after the reaction is referred to as a dental mucosa adjusting material.
[0076]
Examples of the dental mucosal preparation kit that can be suitably used in the above production method include the following (I) and (II).
[0077]
(I) Two types of compositions 1 (COMP-1) for dental mucosa-adjusting materials and 2 compositions (COMP-) for dental mucosa-adjusting materials satisfying the following conditions (1), (2), and (3) A kit for a dental mucosa-adjusting material, comprising the combination of 2).
(1) The COMP-1 and the COMP-2 include at least one component selected from the component (A), the component (B), the component (C), and the component (D).
(2) The combination of COMP-1 and COMP-2 includes all the components (A) to (D), and the amount ratio of each component in the combination is:
Component (A): 100 parts by weight
Component (B): Total number of unsaturated bonds of component (A) {[C = C]_A} The total number of hydrogen atoms bonded to the silicon atom in component (B) for {{SiH]_B} Ratio {[SiH]_B/ [C = C]_A}, An amount of 0.5 to 1.5,
Component (C): 1 to 300 parts by weight, and
Component (D): catalyst amount
It is.
(3) Component (B) and component (D) do not coexist in either COMP-1 or COMP-2.
[0078]
  (II) Two types of dental mucosa-adjusting composition 3 (COMP-3) and dental mucosal-adjusting composition 4 (COMP-) that satisfy the following conditions (1), (2), and (3) A kit for a dental mucosa-adjusting material, comprising the combination of 4).
(1) COMP-3 and the COMP-4 includes at least one component selected from the component (A), the component (B), the component (F), the component (C), and the component (D).
(2) The combination of COMP-3 and COMP-4 includes all the components (A) to (D) and component (F), and the amount of each component in the combination The ratio is
Component (A): 100 parts by weight
Component (B) and Component (F): Total number of unsaturated bonds of component (A) {[C = C], respectively_A} The total number of hydrogen atoms bonded to the silicon atom in the component (B) {[SiH]_B} And the total number of hydrogen atoms bonded to silicon atoms in component (F) {[SiH]_F} To the sum ratio {([SiH]_B+ [SiH]_F) / [C = C]_A} And [SiH]_BAnd [SiH]_FRatio {[SiH]_F/ [SiH]_B} And ([SiH]_B+ [SiH]_F) / [C = C]_A0.5 to 5 and [SiH]_F/ [SiH]_BIs an amount of 0.5-10,
Component (C): 1 to 300 parts by weight, and
Component (D): catalyst amount
It is.
(3) Component (D), component (B) and / or component (F) do not coexist in either COMP-3 or COMP-4.
[0079]
Further, the preferred ratio of (I) to (2) is [SiH]._B/ [C = C]_AIs a quantity ratio of 0.7 to 1.5, and a suitable quantity ratio in (2) of (II) above is ([SiH]_B+ [SiH]_F) / [C = C]_A1.0-3.0 and [SiH]_F/ [SiH]_BIs a quantitative ratio of 0.8 to 5.0.
[0080]
In addition, in each of the above-described dental mucosal preparation material kits, as long as the conditions shown in (1) to (3) are satisfied, the components for each dental mucosal preparation material constituting the kit are included. You may mix | blend various fillers and various additives other than (E) and a silica type filler suitably.
[0081]
The preparation method of each composition for dental mucosa-adjusting material constituting the kit for dental mucosa-adjusting material is not particularly limited, and component (A), component (B), component (C), component (D), component Appropriate amounts of necessary components are weighed out of (E), component (F), and various fillers and additives, and kneaded until they are uniform by a general kneader such as a kneader or planetary, or a general stirrer. By stirring, a paste-like or liquid composition can be obtained.
[0082]
When producing the dental mucosa preparation material of the present invention, a predetermined amount of the two types of dental mucosa preparation material composition is weighed immediately before use, and after kneading, it is placed on the back surface of the denture with a pre-applied adhesive. It is hold | maintained until it fully hardens | cures in an oral cavity, It should just take out from the intraoral area after hardening and remove an excess part.
[0083]
As the adhesive, it is preferable to use a silicone-modified acrylic copolymer adhesive described in JP-A-7-70246, JP-A-7-76611, and the like.
[0084]
【Example】
Examples are provided to describe the present invention more specifically, but the present invention is not limited to these examples.
[0085]
The organopolysiloxanes used in the following examples are summarized in Table 1.
[0086]
[Table 1]

In the following examples and comparative examples, the evaluation of the dental mucosa adjusting material was performed by the following method, and the same value was measured three times for the same sample and the average value was recorded.
[0087]
(1) Sine tangent (tan δ): A strip-shaped cured body is prepared and stored in 37 ° C. water for 2 hours, and then measured using a dynamic viscoelasticity measuring device at 37 ° C. and 1 Hz under a tensile load. The sine tangent was determined.
[0088]
(2) Elastic strain: A cured product having a diameter of 13 mm and a height of 20 mm was prepared, stored in 37 ° C. water for 2 hours, and then allowed to stand in a room at 23 ° C. for 5 minutes. Thereafter, the elastic strain was measured according to the following method. .
[0089]
First, a load of 10 kPa is applied, and the height when 30 seconds have elapsed is read (A). After 30 seconds, an additional load is applied over 10 seconds so that the total load becomes 100 kPa, and the height 30 seconds after the end of the load is read (B). The elastic strain is calculated from these measured values by the following formula.
Elastic strain (%) = (A−B) ÷ 20 × 100
(3) Permanent distortion: A cured product having a diameter of 13 mm and a height of 20 mm was prepared, stored in 37 ° C. water for 2 hours, and then allowed to stand in a room at 23 ° C. for 5 minutes. Thereafter, permanent distortion was measured according to the following method. .
[0090]
First, a load of 4 kPa is applied, and the height when 25 seconds have elapsed is read (C). Then, 12% (2.4 mm) deformation is applied over 5 seconds and held for 30 seconds. And after making it a no-load state for 30 seconds, the load of 4 kPa is applied again and the height after 30 seconds is read (D). From these measured values, permanent distortion is calculated from the following equation.
Permanent distortion (%) = (C−D) ÷ 20 × 100
(4) Shore hardness: A cured product having a diameter of 9 mm and a height of 12 mm was prepared and stored in 37 ° C. water for 2 hours. Then, it left still in a 23 degreeC room | chamber interior for 5 minutes, the load of 9.8N was applied with the spring type hardness tester (A type), and the value when 30 second passed was made into the Shore hardness.
[0091]
(5) Coloring amount: 10 mm × 10 mm × 2 mm cured body was prepared, stored in 37 ° C. water for 2 hours, and then before coloring by a color difference meter^*, A^*, B^*Measure. Thereafter, the test piece is immersed in a 5 wt% aqueous coffee solution and stored at 40 ° C. for 24 hours while stirring. After storage, wash with water, dry, and again with a color difference meter^*, A^*, B^*And the difference between them, ΔL^*, Δa^*, Δb^*From the following equation, the coloring amount (ΔE^*)
Coloring amount (ΔE^*) = {(ΔL^*)²+ (Δa^*)²+ (Δb^*)²}^1/2
(6) Stability over time of physical properties: The elastic strain, permanent strain and Shore hardness after the sample is stored in 37 ° C. water for 7 days are measured according to the above (2), (3) and (4).
[0092]
(7) Evaluation of ease of removal from denture base: After applying an adhesive to a resin plate produced in the same manner as the denture base, a dental mucosa conditioning material was placed on the adhesive application surface and cured. . After storing in 37 ° C. water for 1 week, the dental mucosa-adjusting material was peeled off from the resin plate with a knife, a dental rotary grinder or the like. The ease of peeling at this time was evaluated in three stages: A: can be easily deleted only with a knife, B: a partial grinding machine is required, and C: can be deleted only with a grinding machine. As for evaluation, A is excellent and C is inferior. As the adhesive, the dental mucosal conditioner of the present invention has the following structural formula
[0093]
[Formula 4]

A 0.5 wt% methylene chloride solution of a copolymer having an average composition represented by the formula (1) was used, and nothing was particularly used for the acrylic mucosa preparation material.
[0094]
Example 1
50 parts by weight of compound a shown in Table 1, 50 parts by weight of compound b, vinylsiloxane complex of platinum in an amount such that platinum is 100 ppm with respect to the total amount of compounds a and b, and 15 parts by weight of dry silica is planetary. And kneaded until uniform to obtain a paste former.
[0095]
50 parts by weight of compound a shown in Table 1, 50 parts by weight of compound b, 2.0 parts by weight of compound e, and 15 parts by weight of dry silica were put in a planetary and kneaded until uniform to obtain paste B.
[0096]
The two types of pastes B and B were kneaded at a mixing ratio of 1: 1 and evaluated according to the evaluation method described above. The results are shown in Table 5.
[0097]
  Examples 2-12
  The materials of each composition shown in Table 2, Table 3 and Table 4 were kneaded by planetary in the same manner as in Example 1 to prepare each paste.Madedid. In addition, the same platinum catalyst as that used in Example 1 was used. Also, in these tables, the surface-treated dry silica means that the dry silica is a silane catalyst such as hexamethyldisilazane.TsuThe surface is treated with a pulling agent.
[0098]
[Table 2]

[0099]
[Table 3]

[0100]
[Table 4]

[0101]
Each paste was tested according to the above evaluation method. The results are shown in Table 5.
[0102]
[Table 5]

Comparative Example 1
The test was conducted according to the above evaluation method using an acrylic mucosa-adjusting material having a composition comprising 120 parts by weight of ethyl methacrylate, 85 parts by weight of butyl butylphthalyl glycolate and 15 parts by weight of ethanol. The results are shown in Table 5.
[0103]
Comparative Example 2
The above evaluation method using an acrylic mucosa-adjusting material having a composition consisting of 110 parts by weight of a butyl methacrylate (90 mol%)-ethyl methacrylate (10 mol%) copolymer and 100 parts by weight of butyl butylphthalyl glycolate The test was conducted according to The results are shown in Table 5.
[0104]
Comparative Example 3
The test was conducted according to the above evaluation method using an acrylic mucosa conditioning material having a composition consisting of 110 parts by weight of a butyl methacrylate (80 mol%)-ethyl methacrylate (20 mol%) copolymer and 100 parts by weight of dibutyl phthalate. went. The results are shown in Table 5.
[0105]
From the results of Table 5, the dental mucosa preparation materials (Examples 1 to 12) of the present invention have sufficient sine tangent (tan δ), elastic strain, permanent strain, and shore hardness throughout 7 days from the intended use. It is retained, and the amount of coloring is small, and removal from the denture base after use is easy. In contrast, the acrylic mucosa conditioners (Comparative Examples 1 to 3) initially have sufficient sine tangent (tan δ), elastic strain, permanent strain, and Shore hardness, but each physical property deteriorates with time. Yes. Moreover, the amount of coloring is large, and removal from the denture base after use is difficult. This shows that the dental mucosa preparation material of the present invention is excellent in terms of durability and workability.
[0106]
【The invention's effect】
The dental mucosa preparation material of the present invention has appropriate viscoelastic properties over a long period of time and can restore the mucosal shape to a natural state with inflammation healing without causing pain to the patient. . In addition, the dental mucosa preparation material of the present invention does not basically use a material that gives a stimulus to a living body, is less contaminated when used on the oral mucosa, and can be easily removed from the denture base after use. It can be removed and has an excellent feature not found in conventional dental mucosa preparation materials.

Claims (7)

 Organopolysiloxane {component (A)} having at least two organic groups having an unsaturated bond at the end thereof, and organohydrogenpolysiloxane having at least three hydrogen atoms bonded to silicon atoms in the molecule A method for producing a dental mucosa-adjusting material, comprising reacting {component (B)} with a hydrosilylation catalyst {component (D)} in the presence of a silica-based filler {component (C)}. Hydrogen whose amount ratio of the component (A) to be reacted and the component (B) is bonded to the silicon atom in the component (B) with respect to the total number of unsaturated bonds {[C = C] _A } of the component ( _A ) The dental mucous membrane according to claim 1 , wherein the dental mucosa is represented by a ratio {[SiH] _B / [C = C] _A } of the total number of atoms {[SiH] _B } of 0.5 to 1.5. A method for manufacturing the adjusting material. The dental mucosa according to claim 2, wherein the reaction is carried out in the presence of an organohydrogenpolysiloxane {component (F)} having two or one hydrogen atom bonded to a silicon atom in the molecule. A method for manufacturing the adjusting material. The amount ratio of the component (A), the component (B), and the component (F) to be reacted is the silicon atom in the component (B) with respect to the total number of unsaturated bonds {[C = C] _A } of the component (A). The ratio of the sum of the total number of bonded hydrogen atoms {[SiH] _B } and the total number of hydrogen atoms bonded to silicon atoms in the component (F) {[SiH] _F } {([SiH] _B + [SiH] _F ) / [C = C] _A } and a ratio of [SiH] _B to [SiH] _F {[SiH] _F / [SiH] _B }, and ([SiH] _B + [SiH] _F ) / [C = C] _A is 0.5 to 5, and [SiH] _F / [SiH] _B is 0.5 to 10, Manufacturing method. The reaction, to claim 1, characterized in that it is carried out in the presence of component (A) organopolysiloxane {component (E)} having no hydrosilylation reactivity of 1-100 parts by weight per 100 parts by weight The manufacturing method of the dental mucosa adjustment material in any one of Claim 4 . Two types of compositions 1 (COMP-1) for dental mucosa-adjusting materials and 2 compositions (COMP-2) for dental mucosa-adjusting materials that satisfy the following conditions (1), (2), and (3) A kit for a dental mucosa-adjusting material, characterized by comprising a combination.
(1) The COMP-1 and the COMP-2 are an organopolysiloxane {component (A)} having at least two organic groups having an unsaturated bond at a terminal, a hydrogen atom bonded to a silicon atom. And at least one component selected from the group consisting of organohydrogenpolysiloxane {component (B)}, silica-based filler {component (C)}, and hydrosilylation catalyst {component (D)} (2) The combination of COMP-1 and COMP-2 includes all the components (A) to (D), and the ratio of each component in the combination is the component (A) : 100 parts by weight, Component (B): Total number of unsaturated bonds {[C = C] _A } of component ( _A ) Total number of hydrogen atoms bonded to silicon atoms in component (B) {[SiH] the ratio of _B} {[ iH] _B / [expressed as C = C] _A}, the amount to be 0.5 to 1.5,
Component (C): 1 to 300 parts by weight, and Component (D): catalytic amount (3) Component (B) and Component (D) do not coexist in either COMP-1 or COMP-2 . Two types of compositions 3 for dental mucosal conditioners (COMP-3) and compositions 4 for dental mucosa conditioners (COMP-4) satisfying the following conditions (1), (2) and (3) A kit for a dental mucosa-adjusting material, characterized by comprising a combination.
(1) The COMP-3 and the COMP-4 are each an organopolysiloxane {component (A)} having at least two organic groups having an unsaturated bond at the terminal, a hydrogen atom bonded to a silicon atom Of at least 3 in the molecule {component (B)}, organohydrogenpolysiloxane having 2 or 1 hydrogen atom bonded to the silicon atom {component (F)} , Silica-based filler {component (C)}, and hydrosilylation catalyst {component (D)} including at least one component (2) In the combination of COMP-3 and COMP-4, All the components (A) to (D) and (F) are included, and the amount ratio of each component in the combination is:
Component (A): 100 parts by weight
Component (B) and Component (F): The total number of hydrogen atoms bonded to silicon atoms in component (B) relative to the total number of unsaturated bonds {[C = C] _A } of component ( _A ) {[ SiH] _B} and the sum ratio of component (F) the total number of hydrogen atoms bonded to the silicon atom in _{{[SiH] F} {(} [SiH] B + [SiH] F) / [C = C ] _A } and the ratio of [SiH] _B and [SiH] _F {[SiH] _F / [SiH] _B }, ([SiH] _B + [SiH] _F ) / [C = C] _A is 0 .5 to 5 and [SiH] _F / [SiH] _B is 0.5 to 10
Component (C): 1 to 300 parts by weight, and Component (D): catalytic amount (3) Component (D), Component (B) and / or Component in any of COMP-3 or COMP-4 Does not coexist with (F)