JP3862797B2 - Dental polishing / repairing agent and dentifrice - Google Patents
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【０００１】
【発明の属する技術分野】
本発明は、歯科用研磨・補修剤（研磨剤・補修剤、以下同じ）組成物及び該歯科用研磨・補修剤を含有してなる歯磨剤に関し、詳しくは歯表面に付着している歯垢の除去作用を有し、且つ歯エナメル質の微小な表面脱灰創に花弁状多孔質リン酸カルシウム系化合物、或いは花弁状多孔質リン酸カルシウム系化合物及び補助剤を含む粉末、顆粒、溶液（懸濁液）又はペーストをすり込むことにより、花弁状多孔質リン酸カルシウム系化合物の再石灰化作用によって表面を強化、保護し、脱灰創を修復する機能を有する歯科用研磨・補修剤組成物及び該歯科用研磨・補修剤を含有してなる歯磨剤に関するものである。
【０００２】
【従来の技術】
虫歯の発生プロセスについては、歯エナメル質の表面に歯垢が沈殿し、その中に生息する微生物が酸を生成し徐々にエナメル質を溶解しエナメル質に微小な創を発生させる（以下、脱灰と記す）。一旦エナメル質が脱灰されると、その後歯磨き操作等により歯垢が除去されても、再び脱灰創に歯垢が付着し、酸による脱灰が繰り返される。このように脱灰、歯垢除去、歯垢再付着、脱灰の繰り返しにより脱灰が進行し肉眼で検知できる虫歯へと進行する。その虫歯を予防するため、または歯清浄化のため従来から歯磨剤が使用されている。
歯磨剤の一般的な基本組成成分は研磨剤３５〜６０重量％、発泡剤０．５〜２重量％、粘着剤０．５〜３重量％、湿潤剤５〜３０重量％、甘味剤０．１〜１重量％、香味剤０．６〜３重量％及び特殊成分０〜３重量％よりなっている。研磨剤としては、例えば炭酸カルシウム、リン酸水素カルシウム２水和物、リン酸水素カルシウム無水物、水酸化アルミニウム、無水ケイ酸、シリカ、ヒドロキシアパタイト等が用いられている。なかでもヒドロキシアパタイトは虫歯の原因となる歯垢を吸着除去するとともに、歯表面に付着し、歯の再石灰化を促進し、歯を強化させる。このため良好な虫歯予防物質として、歯磨き組成物に配合されている。
【０００３】
【発明が解決しようとする課題】
ところで、従来の研磨剤は、機械的に研磨をする事により歯垢の除去を行うので、健全な歯表面を損なうという問題点があり、またこのように機械的に除去した歯垢は、研磨中に歯のエナメル質に一部が再吸着してしまうという問題点があった。
【０００４】
特開昭５５−５７５１４号においてヒドロキシアパタイト粉末を含み、且つ微酸性ないし弱酸性に保った歯磨剤組成物が報告されている。しかしながら、粒子形状が板状、針状、鱗片状であるため、歯間、れっこう部等の歯ブラシが届かない部位の歯垢の除去は困難である。また上記の板状、針状、鱗片状の結晶構造であるために、その形状に起因して表面の損傷が問題となっていた。
【０００５】
【課題を解決するための手段】
本発明者等は、上記課題を解決するべく鋭意研究の結果、特定の製造方法で得られる、特定の粒子形状を有する粒子が所期の目的の歯科用研磨・補修剤としての機能を有し、また該歯科用研磨・補修剤を含有してなる歯磨剤が所期の目的の機能を有していることを見いだし、本発明を完成した。
【０００６】
本発明の第一は、核材となる炭酸カルシウムの水懸濁液分散体とリン酸の希釈水溶液及び／又はリン酸水素カルシウムの水懸濁液分散体及び／又はリン酸水素カルシウム二水塩の水懸濁液分散体をＣａ／Ｐの原子比が１６．７以下の割合で中性領域において反応させることにより得られる、炭酸カルシウムを核材とする花弁状多孔質構造を有するリン酸カルシウム系化合物からなり、Ｃａ／Ｐの原子比が１６．７以下であり、且つ下記の式（ａ）〜（ｇ）を満足することを特徴とする歯科用研磨・補修剤を内容とするものである。
（ａ）０．０１≦ｄｘ１≦１（μｍ）
（ｂ）９５≦ω１≦９９（％）
（ｃ）７０≦ω２≦９５（％）
（ｄ）５０≦Ｓｗ１≦５００（m2／ｇ）
（ｅ）０．１≦ｄｘ２≦２０（μｍ）
（ｆ）１≦α≦５ 但し α＝ｄ５０／ｄｘ２
（ｇ）０≦β≦８ 但し β＝（ｄ９０−ｄ１０）／ｄ５０
但し、
ｄｘ１：水銀圧入法により測定した細孔分布により求めた粒子の平均細孔径（μｍ）
ω１ ：ＪＩＳＫ５１０１−９１ ２０．１ 顔料試験方法の静置法による見掛け比容（ ml／ｇ）を測定し、下記の式（ｈ）により計算した静置空隙率（％）
１
（ｈ）ω１＝｛１−─────────────｝×１００（％）
２．９×［見掛け比容］
ω２：試料０．５ｇを断面積２cm2 の円筒に充填、３０kg／cm2 の圧力で３０秒間加圧、 その厚みをノギスで測定し、下記の式（ｉ）より計算した３０kg／cm2 の加圧空隙 率（％）
０．５
（ｉ）ω２＝｛１−────────────｝×１００（％）
２．９×２×［厚さ］
Ｓｗ１：窒素吸着法によるＢＥＴ比表面積（m2／ｇ）
ｄｘ２：電子顕微鏡写真により測定した粒子の平均粒子径（μｍ）
α ：分散係数
ｄ５０：マイクロトラックＦＲＡレーザー式粒度分布計により測定した粒子の５０％平均 粒子径（μｍ）
β ：シャープネス
ｄ９０：マイクロトラックＦＲＡレーザー式粒度分布計により測定した粒子のふるい通過 側累計９０％粒子径（μｍ）
ｄ１０：マイクロトラックＦＲＡレーザー式粒度分布計により測定した粒子のふるい通過 側累計１０％粒子径（μｍ）
【０００７】
本発明の歯科用研磨・補修剤の重要な特徴は粒子形状にあり、単なるリン酸カルシウム系化合物ではなく、花弁状構造を有する多孔質リン酸カルシウム系化合物で構成されていることにある。
本発明の歯科用研磨・補修剤は、その花弁状構造が自己崩壊性（外部からの応力が粒子に作用した場合、粒子の一部が破壊又は崩壊変形することにより、外部からの応力を粒子自身が自己吸収又は自己分散し、その結果粒子外部に対する粒子からの反発力が低下する性質）を有しているため、例えば本発明の歯科用研磨・補修剤を用いて歯を研磨した場合、エナメル質との接触の際、花弁状構造の粒子が自己破壊するため、接触により発生する応力を大きく軽減させることができ、自己破壊性を有しない他の塊状粒子を用いた場合と比較して、歯表面に傷を生じさせる度合いは著しく低下し、その結果歯を傷つけることなく歯垢を除去する事ができる。また研磨により破壊された粒子は歯表面の脱灰創に結合され、唾液で再石灰化し、歯表面の強化、保護及び虫歯の初期状況である脱灰創を修復する歯科用研磨・補修剤を提供することができる。
【０００８】
本発明の第二は、上記歯科用研磨・補修剤を含有してなる歯磨剤である。本発明の歯科用研磨・補修剤を含有させることにより歯表面を傷つけることなく研磨でき、また脱灰創を修復できる歯磨剤を提供することができる。
以下に本発明を詳述する。
【０００９】
本発明の歯科用研磨・補修剤を構成する花弁状多孔質リン酸カルシウム系化合物としては特に制限はないが、非晶質リン酸カルシウム〔略号ＡＣＰ、化学式Ｃａ3 （ＰＯ4 ）2 ・ｎＨ2 Ｏ〕、フッ素アパタイト〔略号ＦＡＰ、化学式Ｃａ10（ＰＯ4 ）6 Ｆ2 〕、塩素アパタイト〔略号ＣＡＰ、化学式Ｃａ10（ＰＯ4 ）6 Ｃｌ2 〕、ヒドロキシアパタイト〔略号ＨＡＰ、化学式Ｃａ10（ＰＯ4 ）6 （ＯＨ）2 〕、リン酸八カルシウム〔略号ＯＣＰ、化学式Ｃａ8 Ｈ2 （ＰＯ4 ）6 ・５Ｈ2 Ｏ〕、リン酸三カルシウム〔略号ＴＣＰ、化学式Ｃａ3 （ＰＯ4 ）2 〕、リン酸水素カルシウム（略号ＤＣＰ、化学式ＣａＨＰＯ4 ）、リン酸水素カルシウム二水和物（略号ＤＣＰＤ、化学式ＣａＨＰＯ4 ・２Ｈ2 Ｏ）等が例示でき、一種又は二種以上でもよく、中でも組成の安定性が高いという観点からヒドロキシアパタイト、リン酸八カルシウム、リン酸三カルシウム、リン酸水素カルシウムが好ましく、ヒドロキシアパタイトが特に好ましい。また、安定性が最も高いヒドロキシアパタイトの含有率に関して言えば、全リン酸カルシウム系化合物に対して１０重量％以上が好ましく、５０重量％がより好ましく、９０重量％が最も好ましい。
【００１０】
本発明の歯科用研磨・補修剤の粒子に占めるＣａ／Ｐの原子比は、１６．７以下であり、歯の再石灰化を効率よく行うという観点から、５．５６以下が好ましく、３．３３以下が更に好ましく、１．８５以下が最も好ましい。Ｃａ／Ｐの下限は生体親和性を維持する観点から１．６０程度が好ましい。また、核材として用いた炭酸カルシウムがすべてリン酸カルシウム系化合物に変化して核材としての炭酸カルシウムが粒子中に存在せず、粒子重量の１００％（Ｃａ／Ｐの原子比は１〜１．６７）が花弁状多孔質リン酸カルシウム系化合物に変化しても何ら問題はない。
【００１１】
本発明の歯科用研磨・補修剤の平均細孔径ｄｘ１は、０．０１≦ｄｘ１≦１である。平均細孔径が０．０１未満の場合、粒子強度が強くなりすぎ研磨時に歯表面を傷つけ、また１を越えた場合、粒子強度が極端に弱くなり研磨時に粒子がほとんど崩壊してしまい十分な研磨ができない。
【００１２】
本発明の歯科用研磨・補修剤の静置空隙率ω１は、９５≦ω１≦９９である。静置空隙率が９５未満の場合、歯垢の吸着量が小さくなり、また９９を越えた場合歯垢の吸着量が大きくなるものの粒子強度が極端に弱くなり研磨時に粒子がほとんど崩壊してしまい十分な研磨ができなくなる。また貯蔵、輸送時の取り扱いが困難になる。
【００１３】
本発明の歯科用研磨・補修剤の加圧空隙率ω２は、７０≦ω２≦９５である。加圧空隙率が７０未満の場合、歯垢の吸着量が小さくなり、また９５を越えた場合歯垢の吸着量が大きくなるものの粒子強度が極端に弱くなり研磨時に粒子がほとんど崩壊してしまい十分な研磨ができなくなる。また貯蔵、輸送時の取り扱いが困難になる。
【００１４】
本発明の歯科用研磨・補修剤のＢＥＴ比表面積Ｓｗ１は、５０≦Ｓｗ１≦５００である。ＢＥＴ比表面積が５０未満の場合、歯垢の吸着量が小さくなり、５００を越えた場合、歯垢の吸着量が大きくなるものの粒子強度が極端に弱くなり研磨時に粒子がほとんど崩壊してしまい十分な研磨ができなくなる。好ましくは１００≦Ｓｗ１≦３５０である。
【００１５】
本発明の歯科用研磨・補修剤の平均粒子径ｄｘ２は、０．１≦ｄｘ２≦２０である。平均粒子径が０．１未満の場合、粒子の凝集により分散性や研磨性能が低下し、また２０を越えた場合、粒子径が大きすぎるためざらつきの原因となる。好ましくは０．２≦ｄｘ２≦１０、更に好ましくは、０．５≦ｄｘ２≦５である。
【００１６】
本発明の歯科用研磨・補修剤の分散係数α及びシャープネスβは、それぞれ１≦α≦５、０≦β≦８である。分散係数が５を越えた場合、粗大な凝集体の割合が多くなり分散性や研磨性能が低下し、また１未満の場合、微細粒子の割合が大きくなり、粒子の凝集性が強まり、研磨性能が低下する。シャープネスが８を越えた場合、粒子径が不均一であると同時に、研磨性能にばらつきを生じる。好ましくは、それぞれ１≦α≦２、０≦β≦３である。
【００１７】
本発明の歯科用研磨・補修剤の調製方法については、例えば核材となる炭酸カルシウムを分散した水系中で、水可溶性リン酸又は水可溶性リン酸塩とを徐々に反応させて、核材表面に花弁状多孔質リン酸カルシウム系化合物を沈降させることにより、本発明の歯科用研磨・補修剤は調製される。具体的には特定の核材となる炭酸カルシウムの水懸濁液分散体とリン酸の希釈水溶液及び／又はリン酸水素カルシウムの水懸濁液分散体及び／又はリン酸水素カルシウム二水塩の水懸濁液分散体をＣａ／Ｐの原子比が１６．７以下の割合で中性領域において混合、特定の熟成条件で熟成後乾燥することにより調製する方法が例示できる。
【００１８】
以下に、花弁状多孔質構造を有するリン酸カルシウム系化合物の内、特に好ましく用いることのできる花弁状多孔質ヒドロキシアパタイトを主成分とする場合における本発明の歯科用研磨・補修剤の調製方法について、より具体的に例示する。
粒度分布測定器（株式会社島津製作所製ＳＡ−ＣＰ３）により測定した平均粒子径が０．１〜５μｍである炭酸カルシウムの水懸濁液分散体とリン酸の希釈水溶液及び／又は粒度分布測定器（株式会社島津製作所製ＳＡ−ＣＰ３）により測定した平均粒子径（μｍ）が２〜１０μｍであるリン酸二水素カルシウムの水懸濁液分散体及び／又は粒度分布測定器（株式会社島津製作所製ＳＡ−ＣＰ３）により測定した平均粒子径（μｍ）が２〜１０μｍであるリン酸水素カルシウム二水塩の水懸濁液分散体をＣａ／Ｐの原子比率が１．６０〜１６．７となる割合で水中で下記の混合条件で混合後、更に下記の熟成条件で熟成を行った後、脱水を行うか又は脱水せずに７００℃以下の乾燥雰囲気下で乾燥し、解砕仕上げを行う。
【００１９】
混合条件
炭酸カルシウムの水懸濁液分散体固形分濃度 １〜１５重量％
リン酸の希釈水溶液濃度 １〜５０重量％
リン酸二水素カルシウムの水懸濁液分散体固形分濃度 ２〜１５重量％
リン酸水素カルシウム二水塩の水懸濁液分散体固形分濃度 ２〜１５重量％
混合時間 ０．１〜１５０時間
混合系水懸濁液温度 ０〜８０℃
混合系の水懸濁液ｐＨ ５〜９
混合系の攪拌羽根周速 ０．５ｍ／秒以上（上限は５０ｍ／秒程度）
熟成条件
熟成系のＣａ濃度 ０．４〜５重量％
熟成時間 ０．１〜１００時間
熟成系水懸濁液温度 ２０〜８０℃
熟成系水懸濁液ｐＨ ６〜９
熟成系の攪拌羽根周速 ０．５ｍ／秒以上（上限は５０ｍ／秒程度）
【００２０】
本発明の歯科用研磨・補修剤は、粒子の分散性，安定性等をさらに高めるために、シランカップリング剤やチタネートカップリング剤等のカップリング剤、有機酸、例えば脂肪酸，樹脂酸，アクリル酸，シュウ酸，クエン酸等の有機酸，酒石酸、フッ酸等の無機酸、それらのポリマー，それらの塩，又はそれらのエステル類等の表面処理剤、界面活性剤やヘキサメタリン酸ソーダ、ピロリン酸、ピロリン酸ソーダ、トリポリリン酸、トリポリリン酸ソーダ、トリメタリン酸、ハイポリリン酸等の縮合リン酸及びその塩等の一種又は２種以上を、常法に従い添加又は表面処理してもさしつかえない。
【００２１】
次に、本発明の歯磨剤は、上記本発明の歯科用研磨・補修剤を配合して得られる。該歯磨剤に配合される他の成分としては特に制限はないが、発泡剤、粘着剤、湿潤剤、甘味剤、香味剤、特殊成分、水等、及び必要に応じて、炭酸カルシウム、水酸化アルミニウム、シリカ等を目的に応じて一種又は二種以上配合される。また花弁状構造を有しない非晶質リン酸カルシウム〔略号ＡＣＰ、化学式Ｃａ3 （ＰＯ4 ）2 ・ｎＨ2 Ｏ〕、アパタイト〔略号ＡＰ、化学式Ｃａ10（ＰＯ4 ）6 Ｘ2 〕、ヒドロキシアパタイト〔略号ＨＡＰ、化学式Ｃａ10（ＰＯ4 ）6 （ＯＨ）2 〕、リン酸八カルシウム〔略号ＯＣＰ、化学式Ｃａ8 Ｈ2 （ＰＯ4 ）6 ・５Ｈ2 Ｏ〕、リン酸三カルシウム〔略号ＴＣＰ、化学式Ｃａ3 （ＰＯ4 ）2 〕、リン酸水素カルシウム（略号ＤＣＰ、化学式ＣａＨＰＯ4 ）、リン酸水素カルシウム二水和物（略号ＤＣＰＤ、化学式ＣａＨＰＯ4 ・２Ｈ2 Ｏ）等の本発明の歯科用研磨・補修剤と異なる、花弁状構造を有しないリン酸カルシウム系化合物を目的に応じて一種又は二種以上配合してもさしつかえない。
本発明の歯磨剤の調製方法については特に制限はないが、常法に従い調製できる。例えば、ニーダー又はその他の混合攪拌機で十分に攪拌し、均一にした後、ロール又はスピードラインミル等で均一に分散させ脱泡する等の調製方法が例示される。また本発明の歯磨剤は、練歯磨剤、粉歯磨剤等に限られるものではない。
【００２２】
【実施例】
以下に本発明を実施例を挙げて更に詳細に説明するが、本発明はこれら実施例のみに限定されるものではない。
尚、以下の記載において、「％」は特に断らない限り、「重量％」を表す。
【００２３】
実施例に使用する炭酸カルシウムの水懸濁液分散体ＡおよびＢの調製方法
炭酸カルシウムの水懸濁液分散体Ａの調製
比重１．０５５で温度が８℃の石灰乳（水酸化カルシウムの水懸濁液）７０００リッターに、炭酸ガス濃度２７重量％の炉ガスを２４m3の流速で導通しｐＨ９まで炭酸化反応を行い、その後４０〜５０℃で５時間撹拌熟成を行う事により粒子間のアルカリを溶出させｐＨ１０．８として分散させ、電子顕微鏡写真より測定した平均粒子径０．０５μｍで粒度分布測定器（株式会社島津製作所製ＳＡ−ＣＰ３）により測定した平均粒子径が０．４８μｍである炭酸カルシウムの水懸濁液分散体Ａを調製した。
【００２４】
炭酸カルシウムの水懸濁液分散体Ｂの調製
丸尾カルシウム株式会社製重質炭酸カルシウム「スーパーＳＳＳ」（１．２m2/g）に水を添加混合後、ＴＫホモミキサー（５０００rpm ，１５分間）にて撹拌分散させて固形分濃度２５％の電子顕微鏡写真より測定した平均粒子径３μｍで粒度分布測定器（株式会社島津製作所製ＳＡ−ＣＰ３）により測定した平均粒子径が３．４μｍである炭酸カルシウムの水懸濁液分散体Ｂを調製した。
【００２５】
実施例１〜６、比較例１〜６
表１及び表２に記載した原料及び混合条件に従い、邪魔板付きステンレスタンクに直径０．６ｍのタービン羽根１枚の撹拌機付きの０．４m3ステンレスタンクに希釈濃度調製及び温調した炭酸カルシウムの水懸濁液分散体を投入し、撹拌下においてリン酸の希釈水溶液，リン酸水素カルシウム二水塩の水懸濁液分散体及びリン酸２水素カルシウムの水懸濁液分散体から選ばれる一種又は二種以上を滴下混合し、表１及び表２に記載した熟成条件に従い撹拌を行いながら熟成した。熟成終了後に撹拌を停止し上澄液をデカンテーション法で取り除き固形分濃度８％に濃縮しスプレ−乾燥を行うことにより、炭酸カルシウムを核材とする花弁状多孔質構造を有するリン酸カルシウム系化合物である、本発明の歯科用研磨・補修剤Ｃ１〜Ｃ６（実施例）、及びＤ１〜Ｄ３（比較例）を調製した。なお、原料及び水の合計重量は４００kgとした。スプレ−乾燥条件は噴霧時の粒径約０．１mm、入り口における熱風温度２５０℃、乾燥時間約１０秒、乾燥直後の乾燥品の２００℃，２時間での加熱減量が５〜８％であった。
【００２６】
実施例１〜６において調製された本発明の歯科用研磨・補修剤Ｃ１〜Ｃ６の物性を表３に示す。また比較例１〜３において調製されたＤ１〜Ｄ３の物性を表４に示す。
さらに、市販の重質炭酸カルシウム（商品名：スーパーＳＳ、丸尾カルシウム株式会社製）、珪酸カルシウム（商品名：フローライトＲ、徳山曹達株式会社製）、及びヒドロキシアパタイト（リン酸三カルシウム、米山化学工業株式会社製）についても物性を比較例４〜６として併記した。
また、Ｃ１の粒子構造を示す電子顕微鏡写真を図１（１０００倍）、図２（１００００倍）に示す。図１、図２より、本発明の歯科用研磨・補修剤は花弁状構造を有することが確認される。図５、６、７に本発明の歯科用研磨・補修剤Ｃ１、Ｃ２、Ｃ３の粉末Ｘ線回折図を示す。図５、６の粉末Ｘ線回折の結果より、Ｃ１、Ｃ２についてはリン酸カルシウム系化合物と炭酸カルシウム（カルサイト）以外は認められなかった。リン酸カルシウム系化合物の主成分はヒドロキシアパタイト（ＨＡＰ）であり、微量のリン酸八カルシウム（ＯＣＰ）を含んでいることが確認できる。
Ｃ３については、図７より炭酸カルシウムは認められず、リン酸カルシウム系化合物以外は認められなかった。リン酸カルシウム系化合物の主成分はヒドロキシアパタイト（ＨＡＰ）であり、微量のリン酸八カルシウム（ＯＣＰ）を含んでいることが確認できる。
尚、本発明の歯科用研磨・補修剤との比較のため、市販のヒドロキシアパタイトの粒子構造を示す電子顕微鏡を図３（１０００倍）、図４（１００００倍）に、また粉末Ｘ線回折図を図８に示す。
図３、図４より、市販のヒドロキシアパタイトは、微細な粒子と該粒子の凝集物であり、花弁状多孔質構造を有するものではないことが確認される。
図８の粉末Ｘ線回折図より、市販のヒドロキシアパタイトは主成分のヒドロキシアパタイト（ＨＡＰ）以外に、微量のリン酸水素カルシウム二水和物（ＤＣＰＤ）を含んでいることが確認される。
表３と表４との対比から明白なように、本発明の歯科用研磨・補修剤は、花弁状構造を持つことにより高い比表面積、空隙率と優れた分散性を持つことが確認できる。
【００２７】
【表１】
【表１】
（表１のつづき）
【表２】
【表３】
【００３１】
【表４】
【００３２】
実施例７〜１２
実施例１〜６で調製したＣ１〜Ｃ６を試料として、表５の配合にて練歯磨剤Ｅ１〜Ｅ６を調製した。
【００３３】
【表５】
比較例７〜１２
比較例１〜３で調製したＤ１〜Ｄ３、比較例４〜６の市販の重質炭酸カルシウム、市販の珪酸カルシウム、市販のヒドロキシアパタイトに変更して用いた以外は実施例７〜１２と同様にして練歯磨剤Ｆ１〜Ｆ６を調製した。
【００３５】
上記実施例１〜６、比較例１〜６で得られた歯科用研磨・補修剤及び実施例７〜１２、比較例７〜１２で得られた歯磨剤について、各種評価を下記の方法で行った。
▲１▼研磨力評価
市販のヒドロキシアパタイトを真空脱気を行いながら圧縮成型し、その後焼結して、直径１．５cm、厚さ１cmの円柱状のヒドロキシアパタイト焼結体を作成した。その表面を８００番のサンドペーパーを用いて均一で、平滑な表面になるように研磨し、その後、蒸留水を流しながら、ブラッシングにより粉末を取り除き、人工歯を得、この人工歯を研磨試験に用いた。
人工歯をブラッシング装置に固定して、試料１．０ｇを用いてブラッシング圧２５０ｇ、１５００回ブラッシングして人工歯の重量減少量（研磨量）の値を研磨力とする。
実施例１〜６で調製した研磨・補修剤Ｃ１〜Ｃ６と比較例１〜３で調製した研磨・補修剤Ｄ１〜Ｄ３、比較例４〜６の市販の重質炭酸カルシウム、市販の珪酸カルシウム、市販のヒドロキシアパタイトの粉体及び純水を用いて上記の研磨力評価方法にて評価した結果を表６に示す。
また、実施例７〜１２で調製したＥ１〜Ｅ６の練歯磨剤と比較例７〜１２で調製したＦ１〜Ｆ６の練歯磨剤及び純水を用いて上記の研磨力評価方法にて評価した結果を表７に示す。
表６、７に示すように、本発明の歯科用研磨・補修剤及び歯磨剤は、花弁状多孔質構造を有しない市販のヒドロキシアパタイトに比べ研磨性能が高く、歯を傷つけることなく歯垢を研磨できることが分かる。
【００３６】
【表６】
【表７】
▲２▼歯垢除去能力評価（１）
上記研磨力評価で用いたのと同じ人工歯を歯垢除去試験に用いた。
人工歯を２４時間口腔内に含み、その後、純水で洗浄して、ブラッシング装置に固定して、試料１．０ｇでブラッシング圧２５０ｇ、１５００回ブラッシングして研磨液中の歯垢量と、人工歯に付着している歯垢量を求めた。歯垢量は、蛋白質量として求めた。
実施例１〜６で調製した研磨・補修剤Ｃ１〜Ｃ６と比較例１〜３で調製した研磨・補修剤Ｄ１〜Ｄ３、及び比較例４〜６の市販の重質炭酸カルシウム、市販の珪酸カルシウム、市販のヒドロキシアパタイトの粉体を用いて上記の歯垢除去能力評価方法にて評価した結果を表８に示す。
また、実施例７〜１２で調製したＥ１〜Ｅ６の練歯磨剤と比較例４〜９で調製したＦ１〜Ｆ６の練歯磨剤を用いて上記の歯垢除去能力評価方法にて評価した結果を表９に示す。
表８、９に示すように本発明の歯科用研磨・補修剤及び歯磨剤は、花弁状多孔質構造を有しない市販のヒドロキシアパタイトと比較し歯垢除去能力が高いことが確認できる。
【００３９】
【表８】
【表９】
▲３▼再石灰化評価
上記研磨力評価で用いたのと同じ人工歯を再石灰化試験に用いた。
長さ１２cm、幅４cm、深さ２cmのアクリル槽の底部に直径１．５cm、深さ０．２cmの人工歯固定用孔５個を設け、この孔に５個の人工歯を固定した。次に、粉体試料１ｇをｐＨ９の０．１Ｍリン酸緩衝液中に懸濁させ、この懸濁液５mlを加えて人工歯を浸し、ゴム膜を介して、人工歯上面を一秒間に１回の速度で回転研磨した。一定時間後人工歯を取り出し、直ちに大量の蒸留水を滴下しつつ洗浄し、ＰＣＳカクテル２mlを加えて、液体シンチレーションカウンターで人工歯に結合した放射能を測定した。ただしヒドロキシアパタイトの結合量は、ヒドロキシアパタイトの比放射能５．４×１０５CPM ／mgとして計算した。実施例１〜６で調製した研磨・補修剤Ｃ１〜Ｃ６、比較例１〜３で調整した研磨・補修剤Ｄ１〜Ｄ３と比較例６の市販のヒドロキシアパタイトの粉体試料を用いて上記の評価方法において評価した結果を表１０に示す。
表１０に示すように本発明の歯科用研磨・補修剤は、花弁状多孔質構造を有しない市販のヒドロキシアパタイトと比較して結合量が多く、優れた再石灰化性能を有することが確認できる。
【００４２】
【表１０】
▲４▼歯垢除去能力評価（２）
健常者ａ〜ｊに、実施例７〜１２で調製したＥ１〜Ｅ６と比較例７〜１２で調製したＦ１〜Ｆ６の練歯磨剤を１週間使用した後、歯に付着した歯垢をかきとり乾燥重量を求めた。尚、試験開始前には、歯間部などを含め歯垢をかきとってきれいにした。その結果を表１１に示す。
【００４４】
【表１１】
▲５▼使用感評価
実施例７〜１２で調製したＥ１〜Ｅ６と比較例７〜１２で調製したＦ１〜Ｆ６の練歯磨剤のブラッシング時のざらつき感を２０名の健常者により５点法で評価した。評価結果を表１２に示す。
表１２により、実施例７〜１２で調製したＥ１〜Ｅ６、比較例９、１２で調製したＦ３、Ｆ６の練歯磨剤はざらつき感が少なく、使用感が良好であることがことが確認された。ただし比較例９、１２で調製したＦ３、Ｆ６の練歯磨剤については表１１より歯垢除去能力が著しく劣ることが確認された。従って、本発明の歯磨剤は優れた性能を有していることが確認できた。
【００４６】
【表１２】
【発明の効果】
本発明の歯科用研磨・補修剤及び歯磨剤は、歯を傷つけることなく歯垢を除去し、また研磨により破壊された粒子は歯表面の脱灰創に結合され、唾液で再石灰化し、歯表面の強化、保護及び虫歯の初期状況である脱灰創を修復することができる。
【図面の簡単な説明】
【図１】実施例１で得られたリン酸カルシウム系化合物粒子Ｃ１の粒子構造を示す電子顕微鏡写真（倍率１０００倍）である。
【図２】実施例１で得られたリン酸カルシウム系化合物粒子Ｃ１の粒子構造を示す電子顕微鏡写真（倍率１００００倍）である。
【図３】比較例６のヒドロキシアパタイトの粒子構造を示す電子顕微鏡写真（倍率１０００倍）である。
【図４】比較例６のヒドロキシアパタイトの粒子構造を示す電子顕微鏡写真（倍率１００００倍）である。
【図５】実施例１で得られたリン酸カルシウム系化合物粒子Ｃ１の粉末Ｘ線回折図である。
【図６】実施例２で得られたリン酸カルシウム系化合物粒子Ｃ２の粉末Ｘ線回折図である。
【図７】実施例３で得られたリン酸カルシウム系化合物粒子Ｃ３の粉末Ｘ線回折図である。
【図８】比較例６の市販のヒドロキシアパタイトの粉末Ｘ線回折図である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a dental polishing / repairing agent (abrasive / repairing agent, the same shall apply hereinafter) composition and a dentifrice containing the dental polishing / repairing agent, and more specifically, plaque adhering to the tooth surface Powder, granule, solution (suspension) containing petal-like porous calcium phosphate compound or petal-like porous calcium phosphate compound and adjuvant on minute surface demineralization wound of tooth enamel Alternatively, a dental polishing / repairing agent composition having a function of strengthening and protecting the surface by remineralizing the petal-like porous calcium phosphate-based compound by rubbing the paste and repairing the decalcified wound, and the dental polishing / The present invention relates to a dentifrice containing a repair agent.
[0002]
[Prior art]
With regard to the caries development process, plaque is deposited on the surface of the tooth enamel, and microorganisms that inhabit it generate acid, gradually dissolve the enamel and generate microscopic wounds in the enamel (hereinafter referred to as delamination). Ash). Once the enamel has been decalcified, even if the plaque is subsequently removed by a brushing operation or the like, the plaque again adheres to the demineralized wound and the decalcification with acid is repeated. In this way, decalcification progresses by repeated decalcification, plaque removal, plaque reattachment, and decalcification, and progresses to caries that can be detected with the naked eye. Dentifrices are conventionally used to prevent the caries or clean the teeth.
The general basic composition of dentifrice is 35-60 wt% abrasive, 0.5-2 wt% foaming agent, 0.5-3 wt% adhesive, 5-30 wt% wetting agent, sweetener 0. It consists of 1 to 1% by weight, flavoring agent 0.6 to 3% by weight and special ingredients 0 to 3% by weight. As the abrasive, for example, calcium carbonate, calcium hydrogen phosphate dihydrate, calcium hydrogen phosphate anhydride, aluminum hydroxide, anhydrous silicic acid, silica, hydroxyapatite and the like are used. Among these, hydroxyapatite adsorbs and removes dental plaque causing caries, adheres to the tooth surface, promotes recalcification of the tooth, and strengthens the tooth. For this reason, it is blended in a toothpaste composition as a good caries preventive substance.
[0003]
[Problems to be solved by the invention]
By the way, the conventional abrasive removes plaque by mechanically polishing, so there is a problem that the sound tooth surface is damaged, and the plaque removed mechanically in this way is polished. There was a problem that a part was re-adsorbed to the enamel of the teeth.
[0004]
JP-A-55-57514 reports a dentifrice composition containing hydroxyapatite powder and kept slightly acidic or weakly acidic. However, since the particle shape is plate-like, needle-like, or scale-like, it is difficult to remove plaque at sites where toothbrushes such as interdental and plaster parts do not reach. In addition, since the plate-like, needle-like, and scale-like crystal structures are used, damage to the surface has been a problem due to the shape.
[0005]
[Means for Solving the Problems]
As a result of earnest research to solve the above problems, the present inventors, Obtained by a specific manufacturing method, Particles having a specific particle shape have a function as a desired dental polishing / repair agent, and a dentifrice containing the dental polishing / repairing agent has a desired function. As a result, the present invention has been completed.
[0006]
The first of the present invention is An aqueous suspension dispersion of calcium carbonate and a dilute aqueous solution of phosphoric acid and / or an aqueous suspension dispersion of calcium hydrogen phosphate and / or an aqueous suspension dispersion of calcium hydrogen phosphate dihydrate as a core material Can be obtained by reacting in the neutral region with a Ca / P atomic ratio of 16.7 or less. It is composed of a calcium phosphate compound having a petal-like porous structure with calcium carbonate as a core material, the Ca / P atomic ratio is 16.7 or less, and the following formulas (a) to (g) are satisfied. It contains the characteristic dental polishing / repairing agent.
(A) 0.01 ≦ dx1 ≦ 1 (μm)
(B) 95 ≦ ω1 ≦ 99 (%)
(C) 70 ≦ ω2 ≦ 95 (%)
(D) 50 ≦ Sw1 ≦ 500 (m 2 / G)
(E) 0.1 ≦ dx2 ≦ 20 (μm)
(F) 1 ≦ α ≦ 5 where α = d50 / dx2
(G) 0 ≦ β ≦ 8 where β = (d90−d10) / d50
However,
dx1: Average pore diameter (μm) of particles determined by pore distribution measured by mercury porosimetry
ω1: JISK5101-91 20.1 The apparent specific volume (ml / g) of the pigment test method by the static method was measured, and the static void ratio (%) calculated by the following formula (h)
1
(H) ω1 = {1 ----------------------- x 100 (%)
2.9 × [apparent specific volume]
ω2: 0.5 g of sample with a cross-sectional area of 2 cm 2 Filled in a cylinder of 30kg /
0.5
(I) ω2 = {1 ------------------------ x 100 (%)
2.9 x 2 x [thickness]
Sw1: BET specific surface area by nitrogen adsorption method (m 2 / G)
dx2: average particle diameter (μm) of particles measured by electron micrograph
α: Dispersion coefficient
d50: 50% average particle diameter (μm) of particles measured by Microtrac FRA laser particle size distribution analyzer
β: Sharpness
d90: 90% cumulative particle diameter (μm) of particles passing through the sieve as measured by Microtrac FRA laser particle size distribution analyzer
d10: 10% particle diameter (μm) of particles passing through the sieve as measured by Microtrac FRA laser particle size distribution analyzer
[0007]
An important feature of the dental polishing / repairing agent of the present invention is in the shape of particles, and is that it is not a simple calcium phosphate compound, but a porous calcium phosphate compound having a petal-like structure.
The dental polishing / repairing agent according to the present invention has a petal-like structure that is self-disintegrating (when external stress acts on the particles, some of the particles are destroyed or collapsed, so that the external stress For example, when the teeth are polished using the dental polishing / repairing agent of the present invention, for example, self-absorbing or self-dispersing, and as a result, the repulsive force from the particles to the outside of the particles is reduced) When contacted with enamel, the petal-like particles are self-destructing, so the stress generated by the contact can be greatly reduced, compared to using other massive particles that do not have self-destructive properties. The degree of scratching on the tooth surface is significantly reduced, and as a result, plaque can be removed without damaging the teeth. In addition, the particles destroyed by polishing are bonded to the demineralized wound on the tooth surface, remineralized with saliva, and a dental polishing / repairing agent that reinforces and protects the tooth surface and restores the decalcified wound, which is the initial state of caries. Can be provided.
[0008]
The second of the present invention is a dentifrice containing the dental polishing / repairing agent. By containing the dental polishing / repairing agent of the present invention, it is possible to provide a dentifrice that can be polished without damaging the tooth surface and can repair decalcified wounds.
The present invention is described in detail below.
[0009]
The petal-like porous calcium phosphate-based compound constituting the dental polishing / repairing agent of the present invention is not particularly limited, but amorphous calcium phosphate [abbreviation ACP, chemical formula Ca Three (PO Four ) 2 ・ NH 2 O], fluorapatite [abbreviation FAP, chemical formula Ca Ten (PO Four ) 6 F 2 ], Chloroapatite [abbreviation CAP, chemical formula Ca Ten (PO Four ) 6 Cl 2 ], Hydroxyapatite [abbreviation HAP, chemical formula Ca Ten (PO Four ) 6 (OH) 2 ], Octacalcium phosphate [abbreviation OCP, chemical formula Ca 8 H 2 (PO Four ) 6 ・ 5H 2 O], tricalcium phosphate [abbreviation TCP, chemical formula Ca Three (PO Four ) 2 ], Calcium hydrogen phosphate (abbreviation DCP, chemical formula CaHPO Four ), Calcium hydrogen phosphate dihydrate (abbreviation DCPD, chemical formula CaHPO) Four ・ 2H 2 O) and the like can be exemplified, and may be one or two or more. Among them, hydroxyapatite, octacalcium phosphate, tricalcium phosphate, and calcium hydrogenphosphate are preferable, and hydroxyapatite is particularly preferable. . In terms of the content of hydroxyapatite having the highest stability, the content is preferably 10% by weight or more, more preferably 50% by weight, and most preferably 90% by weight based on the total calcium phosphate compound.
[0010]
The atomic ratio of Ca / P in the particles of the dental polishing / repairing agent of the present invention is 16.7 or less, and preferably 5.56 or less from the viewpoint of efficiently performing remineralization of teeth. 33 or less is more preferable, and 1.85 or less is most preferable. The lower limit of Ca / P is preferably about 1.60 from the viewpoint of maintaining biocompatibility. Further, all the calcium carbonate used as the core material is changed to a calcium phosphate compound so that the calcium carbonate as the core material does not exist in the particles, and 100% of the particle weight (Ca / P atomic ratio is 1-1.67). ) May be changed to a petal-like porous calcium phosphate compound.
[0011]
The average pore diameter dx1 of the dental polishing / repairing agent of the present invention is 0.01 ≦ dx1 ≦ 1. If the average pore diameter is less than 0.01, the particle strength becomes too strong, and the tooth surface is damaged during polishing. If it exceeds 1, the particle strength becomes extremely weak and the particles are almost completely collapsed during polishing. I can't.
[0012]
The static porosity ω1 of the dental polishing / repairing agent of the present invention is 95 ≦ ω1 ≦ 99. When the static porosity is less than 95, the amount of plaque adsorbed is small, and when it exceeds 99, the amount of adsorbed plaque increases, but the particle strength becomes extremely weak and the particles are almost collapsed during polishing. Sufficient polishing is not possible. In addition, handling during storage and transportation becomes difficult.
[0013]
The pressurized porosity ω2 of the dental polishing / repairing agent of the present invention is: 7 0 ≦ ω2 ≦ 95. When the pressure void ratio is less than 70, the amount of plaque adsorbed becomes small. When it exceeds 95, the amount of adsorbed plaque increases, but the particle strength becomes extremely weak and the particles are almost collapsed during polishing. Sufficient polishing is not possible. In addition, handling during storage and transportation becomes difficult.
[0014]
The BET specific surface area Sw1 of the dental polishing / repairing agent of the present invention is 50 ≦ Sw1 ≦ 500. If the BET specific surface area is less than 50, the amount of adsorbed plaque will be small. If it exceeds 500, the amount of adsorbed plaque will be large, but the particle strength will be extremely weak and the particles will be almost collapsed during polishing. It becomes impossible to polish smoothly. Preferably 100 ≦ Sw1 ≦ 350.
[0015]
The average particle diameter dx2 of the dental polishing / repairing agent of the present invention is 0.1 ≦ dx2 ≦ 20. When the average particle size is less than 0.1, the dispersibility and polishing performance are deteriorated due to aggregation of the particles. When the average particle size exceeds 20, the particle size is too large, which causes roughness. Preferably 0.2 ≦ dx2 ≦ 10, and more preferably 0.5 ≦ dx2 ≦ 5.
[0016]
The dispersion coefficient α and sharpness β of the dental polishing / repairing agent of the present invention are 1 ≦ α ≦ 5 and 0 ≦ β ≦ 8, respectively. When the dispersion coefficient exceeds 5, the proportion of coarse aggregates increases and the dispersibility and polishing performance decrease. When the dispersion coefficient is less than 1, the proportion of fine particles increases and the agglomeration of particles increases and the polishing performance increases. Decreases. When the sharpness exceeds 8, the particle size is not uniform and the polishing performance varies. Preferably, 1 ≦ α ≦ 2 and 0 ≦ β ≦ 3, respectively.
[0017]
About the preparation method of the dental polishing / repairing agent of the present invention Is For example, in a water system in which calcium carbonate as a core material is dispersed, water-soluble phosphoric acid or water-soluble phosphate is gradually reacted to precipitate the petal-like porous calcium phosphate compound on the core material surface. The inventive dental polishing / repairing agent is prepared. Specifically, an aqueous suspension of calcium carbonate and a dilute aqueous solution of phosphoric acid and / or an aqueous suspension of calcium hydrogenphosphate and / or calcium hydrogenphosphate dihydrate as a specific core material Water suspension dispersion Ca / P atomic ratio of 16.7 or less At a rate of Neutral region The method of preparing by mixing and drying after aging under specific aging conditions can be exemplified.
[0018]
Hereinafter, among the calcium phosphate compounds having a petal-like porous structure, the preparation method of the dental polishing / repairing agent of the present invention in the case where the petal-like porous hydroxyapatite that can be used particularly preferably is the main component. Specific examples will be given.
A water suspension dispersion of calcium carbonate and a dilute aqueous solution of phosphoric acid and / or a particle size distribution measuring device having an average particle size of 0.1 to 5 μm measured by a particle size distribution measuring device (SA-CP3 manufactured by Shimadzu Corporation). An aqueous suspension dispersion of calcium dihydrogen phosphate and / or a particle size distribution measuring instrument (manufactured by Shimadzu Corporation) having an average particle diameter (μm) measured by (SA-CP3 manufactured by Shimadzu Corporation) is 2 to 10 μm. An aqueous suspension dispersion of calcium hydrogenphosphate dihydrate having an average particle size (μm) measured by SA-CP3) of 2 to 10 μm has an atomic ratio of Ca / P of 1.60 to 16.7. After mixing in water in the proportions under the following mixing conditions and further aging under the following aging conditions, dehydration is performed or drying is performed in a dry atmosphere of 700 ° C. or lower without dehydration, and crushing finish is performed.
[0019]
Mixing conditions
Calcium carbonate aqueous suspension dispersion solid content concentration 1-15 wt%
1-50% by weight of dilute aqueous solution of phosphoric acid
Calcium dihydrogen phosphate aqueous suspension dispersion solids concentration 2-15% by weight
Calcium hydrogen phosphate dihydrate aqueous suspension dispersion solid content concentration 2 to 15% by weight
Mixing time 0.1-150 hours
Mixing system water suspension temperature 0-80 ° C
Water suspension pH of mixed system 5-9
Stirring blade peripheral speed of mixed system 0.5m / second or more (upper limit is about 50m / second)
Aging conditions
Aging Ca concentration 0.4 to 5 wt%
Aging time 0.1-100 hours
Aging water suspension temperature 20-80 ° C
Aged aqueous suspension pH 6-9
Aging impeller peripheral speed 0.5 m / sec or more (upper limit is about 50 m / sec)
[0020]
The dental polishing / repairing agent of the present invention is used to further improve the dispersibility and stability of particles, coupling agents such as silane coupling agents and titanate coupling agents, organic acids such as fatty acids, resin acids, acrylics. Surface treatment agents such as acids, organic acids such as oxalic acid and citric acid, inorganic acids such as tartaric acid and hydrofluoric acid, polymers, salts and esters thereof, surfactants, sodium hexametaphosphate, pyrophosphate One or two or more of condensed phosphoric acid such as sodium pyrophosphate, tripolyphosphoric acid, sodium tripolyphosphoric acid, trimetaphosphoric acid, and high polyphosphoric acid and salts thereof may be added or surface-treated according to a conventional method.
[0021]
Next, the dentifrice of the present invention is obtained by blending the dental polishing / repairing agent of the present invention. There are no particular restrictions on the other ingredients included in the dentifrice, but foaming agents, adhesives, wetting agents, sweeteners, flavoring agents, special ingredients, water, etc., and, if necessary, calcium carbonate, hydroxide One or two or more of aluminum, silica and the like are blended depending on the purpose. Amorphous calcium phosphate having no petal-like structure [abbreviation ACP, chemical formula Ca Three (PO Four ) 2 ・ NH 2 O], apatite [abbreviation AP, chemical formula Ca Ten (PO Four ) 6 X 2 ], Hydroxyapatite [abbreviation HAP, chemical formula Ca Ten (PO Four ) 6 (OH) 2 ], Octacalcium phosphate [abbreviation OCP, chemical formula Ca 8 H 2 (PO Four ) 6 ・ 5H 2 O], tricalcium phosphate [abbreviation TCP, chemical formula Ca Three (PO Four ) 2 ], Calcium hydrogen phosphate (abbreviation DCP, chemical formula CaHPO Four ), Calcium hydrogen phosphate dihydrate (abbreviation DCPD, chemical formula CaHPO) Four ・ 2H 2 Different from the dental polishing / repairing agent of the present invention such as O), one or more calcium phosphate compounds having no petal-like structure may be blended depending on the purpose.
Although there is no restriction | limiting in particular about the preparation method of the dentifrice of this invention, It can prepare according to a conventional method. For example, after sufficiently stirring and homogenizing with a kneader or other mixing stirrer, a preparation method such as uniform dispersion with a roll or a speed line mill or the like and defoaming is exemplified. The dentifrice of the present invention is not limited to a toothpaste, a powder dentifrice or the like.
[0022]
【Example】
Examples The present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples.
In the following description, “%” represents “% by weight” unless otherwise specified.
[0023]
Methods for preparing aqueous suspension dispersions A and B of calcium carbonate used in the examples
Preparation of aqueous dispersion A of calcium carbonate suspension
24 m of furnace gas with a carbon dioxide concentration of 27% by weight is applied to 7000 liters of lime milk (calcium hydroxide aqueous suspension) at a specific gravity of 1.055 and a temperature of 8 ° Three The average particle size measured from an electron micrograph was obtained by conducting a carbonation reaction up to pH 9 and conducting a carbonation reaction until pH 9 followed by stirring and aging at 40 to 50 ° C. for 5 hours to elute alkali between particles and disperse them as pH 10.8. An aqueous suspension A of calcium carbonate having an average particle size of 0.48 μm measured by a particle size distribution analyzer (SA-CP3 manufactured by Shimadzu Corporation) at 0.05 μm was prepared.
[0024]
Preparation of aqueous dispersion B of calcium carbonate
Heavy calcium carbonate "Super SSS" manufactured by Maruo Calcium Co., Ltd. (1.2m 2 / g), after adding and mixing water, the mixture was stirred and dispersed with a TK homomixer (5000 rpm, 15 minutes) and measured with an average particle size of 3 μm measured by an electron micrograph having a solid content concentration of 25% (Shimadzu Corporation) An aqueous suspension B of calcium carbonate having an average particle size of 3.4 μm measured by SA-CP3) manufactured by Seisakusho was prepared.
[0025]
Examples 1-6, Comparative Examples 1-6
In accordance with the raw materials and mixing conditions described in Table 1 and Table 2, 0.4 m with a stirrer with one turbine blade having a diameter of 0.6 m in a stainless steel tank with baffle plates Three A stainless steel tank is charged with a dilute concentration adjusted and temperature-controlled aqueous dispersion of calcium carbonate, and with stirring, a dilute aqueous solution of phosphoric acid, an aqueous suspension of calcium hydrogen phosphate dihydrate, and phosphoric acid 2 One or two or more selected from aqueous dispersions of calcium hydrogen were dropped and mixed, and aged with stirring according to the aging conditions described in Tables 1 and 2. After completion of ripening, the stirring is stopped, the supernatant is removed by decantation, concentrated to a solid content of 8%, and spray-dried to obtain a calcium phosphate compound having a petal-like porous structure with calcium carbonate as a core material. Certain dental polishing / repairing agents C1 to C6 (Examples) and D1 to D3 (Comparative Examples) of the present invention were prepared. The total weight of the raw material and water was 400 kg. The spray-drying conditions were such that the particle size at spraying was about 0.1 mm, the hot air temperature at the entrance was 250 ° C., the drying time was about 10 seconds, and the heat loss at 200 ° C. for 2 hours immediately after drying was 5-8%. It was.
[0026]
Table 3 shows the physical properties of the dental polishing / repairing agents C1 to C6 of the present invention prepared in Examples 1 to 6. Table 4 shows the physical properties of D1 to D3 prepared in Comparative Examples 1 to 3.
Furthermore, commercially available heavy calcium carbonate (trade name: Super SS, manufactured by Maruo Calcium Co., Ltd.), calcium silicate (trade name: Florite R, manufactured by Tokuyama Soda Co., Ltd.), and hydroxyapatite (tricalcium phosphate, Yoneyama Chemical) The physical properties of Kogyo Kogyo Co., Ltd. are also shown as Comparative Examples 4-6.
Moreover, the electron micrograph which shows the particle structure of C1 is shown in FIG. 1 (1000 times) and FIG. 2 (10000 times). 1 and 2, it is confirmed that the dental polishing / repairing agent of the present invention has a petal-like structure. 5, 6 and 7 show powder X-ray diffraction patterns of the dental polishing / repairing agents C1, C2 and C3 of the present invention. From the results of the powder X-ray diffraction in FIGS. 5 and 6, C1 and C2 other than the calcium phosphate compound and calcium carbonate (calcite) were not recognized. It can be confirmed that the main component of the calcium phosphate compound is hydroxyapatite (HAP) and contains a small amount of octacalcium phosphate (OCP).
For C3, calcium carbonate was not observed from FIG. 7, and other than calcium phosphate compounds were not recognized. It can be confirmed that the main component of the calcium phosphate compound is hydroxyapatite (HAP) and contains a small amount of octacalcium phosphate (OCP).
For comparison with the dental polishing / repairing agent of the present invention, an electron microscope showing the particle structure of commercially available hydroxyapatite is shown in FIG. 3 (1000 times) and FIG. 4 (10000 times), and a powder X-ray diffraction diagram. Is shown in FIG.
3 and 4, it is confirmed that the commercially available hydroxyapatite is a fine particle and an aggregate of the particle and does not have a petal-like porous structure.
From the powder X-ray diffraction pattern of FIG. 8, it is confirmed that commercially available hydroxyapatite contains a trace amount of calcium hydrogen phosphate dihydrate (DCPD) in addition to the main component hydroxyapatite (HAP).
As is clear from the comparison between Table 3 and Table 4, it can be confirmed that the dental polishing / repairing agent of the present invention has a high specific surface area, porosity and excellent dispersibility by having a petal-like structure.
[0027]
[Table 1]
[Table 1]
(Continued from Table 1)
[Table 2]
[Table 3]
[0031]
[Table 4]
[0032]
Examples 7-12
Toothpastes E1 to E6 were prepared with the formulations shown in Table 5 using C1 to C6 prepared in Examples 1 to 6 as samples.
[0033]
[Table 5]
Comparative Examples 7-12
Except having changed into D1-D3 prepared in Comparative Examples 1-3, commercially available heavy calcium carbonate of Comparative Examples 4-6, commercially available calcium silicate, and commercially available hydroxyapatite, it was carried out similarly to Examples 7-12. Toothpastes F1 to F6 were prepared.
[0035]
The dental polishing / repairing agents obtained in Examples 1-6 and Comparative Examples 1-6 and the dentifrices obtained in Examples 7-12 and Comparative Examples 7-12 are subjected to various evaluations by the following methods. It was.
(1) Polishing power evaluation
A commercially available hydroxyapatite was compression-molded while performing vacuum degassing, and then sintered to prepare a cylindrical hydroxyapatite sintered body having a diameter of 1.5 cm and a thickness of 1 cm. The surface is polished using a # 800 sandpaper so that the surface is uniform and smooth. Then, while flowing distilled water, the powder is removed by brushing to obtain an artificial tooth. Using.
The artificial tooth is fixed to a brushing device, and a brushing pressure of 250 g and a brushing of 1500 times are performed using a sample of 1.0 g, and the weight reduction amount (polishing amount) of the artificial tooth is defined as the polishing power.
Polishing / repairing agents C1-C6 prepared in Examples 1-6 and polishing / repairing agents D1-D3 prepared in Comparative Examples 1-3, commercially available heavy calcium carbonate of Comparative Examples 4-6, commercially available calcium silicate, Table 6 shows the results of evaluation by the above-described polishing power evaluation method using commercially available hydroxyapatite powder and pure water.
Moreover, the result evaluated by said grinding | polishing power evaluation method using the toothpaste of E1-E6 prepared in Examples 7-12, the toothpaste of F1-F6 prepared in Comparative Examples 7-12, and a pure water. Is shown in Table 7.
As shown in Tables 6 and 7, the dental polishing / repairing agent and dentifrice of the present invention have higher polishing performance than commercially available hydroxyapatite that does not have a petal-like porous structure, and can prevent plaque from being damaged. It can be seen that it can be polished.
[0036]
[Table 6]
[Table 7]
(2) Evaluation of plaque removal ability (1)
The same artificial teeth used in the polishing power evaluation were used in the plaque removal test.
Artificial teeth are included in the oral cavity for 24 hours, then washed with pure water, fixed to a brushing device, brushed with a sample of 1.0 g, brushing pressure of 250 g, 1500 times, and the amount of plaque in the polishing liquid, artificial The amount of plaque adhering to the teeth was determined. The amount of plaque was determined as the amount of protein.
Polishing / repairing agents C1 to C6 prepared in Examples 1 to 6, polishing / repairing agents D1 to D3 prepared in Comparative Examples 1 to 3, and commercially available heavy calcium carbonate of Comparative Examples 4 to 6, commercially available calcium silicate Table 8 shows the results of evaluation using the above-described plaque removal ability evaluation method using commercially available hydroxyapatite powder.
Moreover, the result evaluated by said plaque removal ability evaluation method using the toothpaste of E1-E6 prepared in Examples 7-12 and the toothpaste of F1-F6 prepared in Comparative Examples 4-9 was used. Table 9 shows.
As shown in Tables 8 and 9, it can be confirmed that the dental polishing / repairing agent and dentifrice of the present invention have a higher plaque removing ability than a commercially available hydroxyapatite having no petal-like porous structure.
[0039]
[Table 8]
[Table 9]
(3) Recalcification evaluation
The same artificial teeth used in the polishing power evaluation were used in the remineralization test.
Five artificial tooth fixing holes having a diameter of 1.5 cm and a depth of 0.2 cm were provided at the bottom of an acrylic tank having a length of 12 cm, a width of 4 cm, and a depth of 2 cm, and five artificial teeth were fixed to the holes. Next, 1 g of a powder sample is suspended in 0.1 M phosphate buffer having a pH of 9, and 5 ml of this suspension is added to immerse the artificial tooth, and the artificial tooth upper surface is placed 1 second per second through the rubber film. Rotated and polished at the speed of rotation. After a certain period of time, the artificial tooth was taken out, immediately washed with a large amount of distilled water added dropwise, 2 ml of PCS cocktail was added, and the radioactivity bound to the artificial tooth was measured with a liquid scintillation counter. However, the amount of hydroxyapatite bound was calculated as the specific activity of hydroxyapatite 5.4 × 10 5 CPM / mg. The above evaluation using the polishing / repairing agents C1 to C6 prepared in Examples 1 to 6, the polishing and repairing agents D1 to D3 prepared in Comparative Examples 1 to 3, and the commercially available hydroxyapatite powder sample of Comparative Example 6 The results evaluated in the method are shown in Table 10.
As shown in Table 10, it can be confirmed that the dental polishing / repairing agent of the present invention has a large amount of binding compared to a commercially available hydroxyapatite having no petal-like porous structure and has excellent remineralization performance. .
[0042]
[Table 10]
(4) Evaluation of plaque removal ability (2)
After using the toothpastes of E1 to E6 prepared in Examples 7 to 12 and F1 to F6 prepared in Comparative Examples 7 to 12 for 1 week on healthy subjects a to j, the plaque adhering to the teeth was scraped off and dried. The weight was determined. Prior to the start of the test, the plaque including the interdental portion was scraped off and cleaned. The results are shown in Table 11.
[0044]
[Table 11]
(5) Usability evaluation
The rough feeling at the time of brushing of the toothpastes of E1 to E6 prepared in Examples 7 to 12 and F1 to F6 prepared in Comparative Examples 7 to 12 was evaluated by 20 healthy subjects by a 5-point method. The evaluation results are shown in Table 12.
From Table 12, it was confirmed that E1 to E6 prepared in Examples 7 to 12 and F3 and F6 toothpastes prepared in Comparative Examples 9 and 12 had little roughness and good usability. . However, for the toothpastes F3 and F6 prepared in Comparative Examples 9 and 12, it was confirmed from Table 11 that the plaque removing ability was remarkably inferior. Therefore, it was confirmed that the dentifrice of the present invention has excellent performance.
[0046]
[Table 12]
【The invention's effect】
The dental polishing / repairing agent and dentifrice of the present invention remove plaque without damaging the teeth, and the particles destroyed by polishing are bonded to the demineralized wound on the tooth surface, remineralized with saliva, It can repair demineralized wounds, the initial condition of surface strengthening, protection and caries.
[Brief description of the drawings]
1 is an electron micrograph (magnification 1000 times) showing the particle structure of calcium phosphate compound particles C1 obtained in Example 1. FIG.
2 is an electron micrograph (magnification 10,000 times) showing the particle structure of calcium phosphate compound particles C1 obtained in Example 1. FIG.
3 is an electron micrograph (magnification 1000 times) showing the particle structure of hydroxyapatite of Comparative Example 6. FIG.
4 is an electron micrograph (magnification 10,000 times) showing the particle structure of hydroxyapatite of Comparative Example 6. FIG.
5 is a powder X-ray diffraction pattern of calcium phosphate compound particles C1 obtained in Example 1. FIG.
6 is a powder X-ray diffraction pattern of calcium phosphate compound particles C2 obtained in Example 2. FIG.
7 is a powder X-ray diffraction pattern of calcium phosphate compound particles C3 obtained in Example 3. FIG.
8 is a powder X-ray diffraction pattern of commercially available hydroxyapatite of Comparative Example 6. FIG.
Claims (10)
（ａ）０．０１≦ｄｘ１≦１（μｍ）
（ｂ）９５≦ω１≦９９（％）
（ｃ）７０≦ω２≦９５（％）
（ｄ）５０≦Ｓｗ１≦５００（m2／ｇ）
（ｅ）０．１≦ｄｘ２≦２０（μｍ）
（ｆ）１≦α≦５ 但し α＝ｄ５０／ｄｘ２
（ｇ）０≦β≦８ 但し β＝（ｄ９０−ｄ１０）／ｄ５０
但し、
ｄｘ１：水銀圧入法により測定した細孔分布により求めた粒子の平均細孔径（μｍ）
ω１ ：ＪＩＳＫ５１０１−９１ ２０．１ 顔料試験方法の静置法による見掛け比容（ ml／ｇ）を測定し、下記の式（ｈ）により計算した静置空隙率（％）
１
（ｈ）ω１＝｛１−─────────────｝×１００（％）
２．９×［見掛け比容］
ω２：試料０．５ｇを断面積２cm2 の円筒に充填、３０kg／cm2 の圧力で３０秒間加圧、 その厚みをノギスで測定し、下記の式（ｉ）より計算した３０kg／cm2 の加圧空隙 率（％）
０．５
（ｉ）ω２＝｛１−────────────｝×１００（％）
２．９×２×［厚さ］
Ｓｗ１：窒素吸着法によるＢＥＴ比表面積（m2／ｇ）
ｄｘ２：電子顕微鏡写真により測定した粒子の平均粒子径（μｍ）
α ：分散係数
ｄ５０：マイクロトラックＦＲＡレーザー式粒度分布計により測定した粒子の５０％平均 粒子径（μｍ）
β ：シャープネス
ｄ９０：マイクロトラックＦＲＡレーザー式粒度分布計により測定した粒子のふるい通過 側累計９０％粒子径（μｍ）
ｄ１０：マイクロトラックＦＲＡレーザー式粒度分布計により測定した粒子のふるい通過 側累計１０％粒子径（μｍ） Calcium carbonate aqueous suspension dispersion and dilute aqueous solution of phosphoric acid and / or calcium hydrogen phosphate aqueous suspension dispersion and / or calcium hydrogen phosphate dihydrate aqueous suspension dispersion as core material Is a calcium phosphate-based compound having a petal-like porous structure with calcium carbonate as a core material , obtained by reacting in a neutral region with a Ca / P atomic ratio of 16.7 or less . A dental polishing / repairing agent having an atomic ratio of 16.7 or less and satisfying the following formulas (a) to (g):
(A) 0.01 ≦ dx1 ≦ 1 (μm)
(B) 95 ≦ ω1 ≦ 99 (%)
(C) 70 ≦ ω2 ≦ 95 (%)
(D) 50 ≦ Sw1 ≦ 500 (m 2 / g)
(E) 0.1 ≦ dx2 ≦ 20 (μm)
(F) 1 ≦ α ≦ 5 where α = d50 / dx2
(G) 0 ≦ β ≦ 8 where β = (d90−d10) / d50
However,
dx1: Average pore diameter (μm) of particles determined by pore distribution measured by mercury porosimetry
ω1: JISK5101-91 20.1 The apparent specific volume (ml / g) of the pigment test method by the static method was measured, and the static void ratio (%) calculated by the following formula (h)
1
(H) ω1 = {1 ----------------------- x 100 (%)
2.9 × [apparent specific volume]
.omega.2: filling the sample 0.5g of cylindrical cross-sectional area 2 cm 2, the pressure for 30 seconds under pressure of 30kg / cm 2, the thickness was measured with calipers, the 30kg / cm 2 was calculated from the equation (i) below Pressurized porosity (%)
0.5
(I) ω2 = {1 ------------------------ x 100 (%)
2.9 x 2 x [thickness]
Sw1: BET specific surface area by nitrogen adsorption method (m 2 / g)
dx2: average particle diameter (μm) of particles measured by electron micrograph
α: Dispersion coefficient d50: 50% average particle diameter (μm) of particles measured by Microtrac FRA laser particle size distribution analyzer
β: Sharpness d90: Particle passing through the sieve as measured by Microtrac FRA laser particle size distribution meter Cumulative 90% particle size (μm)
d10: 10% particle diameter (μm) of particles passing through the sieve as measured by Microtrac FRA laser particle size distribution analyzer
（ｊ）１００≦Ｓｗ１≦３５０（m2／ｇ）The dental polishing / repairing agent according to claim 1, wherein the BET specific surface area Sw1 comprises particles satisfying the following formula (j).
(J) 100 ≦ Sw1 ≦ 350 (m 2 / g)
（ｋ）０．２≦ｄｘ２≦１０（μｍ）The dental polishing / repairing agent according to claim 1 or 2, comprising an average particle size dx2 satisfying the following formula (k).
(K) 0.2 ≦ dx2 ≦ 10 (μm)
（ｌ）０．５≦ｄｘ２≦５（μｍ）The dental polishing / repairing agent according to any one of claims 1 to 3, wherein the average particle size dx2 comprises particles satisfying the following formula (l).
(L) 0.5 ≦ dx2 ≦ 5 (μm)
（ｍ）１≦α≦２
（ｎ）０≦β≦３The dental polishing / repairing agent according to any one of claims 1 to 4, comprising a particle having a dispersion coefficient α and a sharpness β that simultaneously satisfy the following formulas (m) and (n).
(M) 1 ≦ α ≦ 2
(N) 0 ≦ β ≦ 3
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP35273596A JP3862797B2 (en) | 1996-12-12 | 1996-12-12 | Dental polishing / repairing agent and dentifrice |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP35273596A JP3862797B2 (en) | 1996-12-12 | 1996-12-12 | Dental polishing / repairing agent and dentifrice |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH10175833A JPH10175833A (en) | 1998-06-30 |
| JP3862797B2 true JP3862797B2 (en) | 2006-12-27 |
Family
ID=18426083
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP35273596A Expired - Lifetime JP3862797B2 (en) | 1996-12-12 | 1996-12-12 | Dental polishing / repairing agent and dentifrice |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3862797B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3971877B2 (en) * | 1999-10-25 | 2007-09-05 | 株式会社サンギ | Oral composition |
| JP2016183066A (en) * | 2015-03-26 | 2016-10-20 | 古手川産業株式会社 | Calcium carbonate composite |
-
1996
- 1996-12-12 JP JP35273596A patent/JP3862797B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH10175833A (en) | 1998-06-30 |
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