JP4493290B2 - Artificial biomaterial and method for producing the same - Google Patents
Artificial biomaterial and method for producing the same Download PDFInfo
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【０００１】
【発明の属する技術分野】
本発明は、生体内に埋め込まれて使用される人工生体材料（インプラント材料）に関する。
詳しくは人工骨、人工関節、人工歯根等の人工生体材料として、有用なコロイダルシリカ粒子付着型人工生体材料とその製造法に関する。
【０００２】
【従来の技術】
従来、骨の欠損部分の代替などでチタン製の人工生体材料が使われている。チタンは人体内においてその表面にリン酸カルシウムが形成（以下石灰化という）されるため、骨組織との親和性が良いことが知られている。
石灰化を促進する手段としては、チタン金属表面のアルカリ処理が知られている。また、チタン金属表面をサンドペーパーにて研磨する方法もある。促進の原因は、ケイ素（Ｓｉ）がチタン表層に移行し、緻密な結晶を形成することによって石灰化が促進されると考えられている。他方、ケイ素またはチタンのアルコキシドを強酸などの処理をして、チタン表面にシリカゲル被膜層などを形成させることにより石灰化が促進されることが知られ、その改良方法が提案されている（例えば、特許文献１〜４参照。）。
しかしながら、この処理では、シリカゲルの被膜層の形成において、高温加熱（４００〜１０００℃）処理を行うため、シリカゲル被膜層の収縮・剥離が促進される。そのため、石灰化能が弱くなり、再現性に乏しく、煩雑な処理となる問題がある。
【０００３】
【特許文献１】
特開平１０−０５２４８４号公報（特許請求の範囲、発明の詳細な説明）
【特許文献２】
特開平１０−０５２４８３号公報（特許請求の範囲、発明の詳細な説明）
【特許文献３】
特開平０６−１６９９８１号公報（特許請求の範囲、発明の詳細な説明）
【特許文献４】
特開平０６−０２３０３０公報（特許請求の範囲、発明の詳細な説明）
【０００４】
【発明が解決しようとする課題】
本発明は、石灰化能に優れ、かつ、チタン表面に対して研磨、熱、アルカリ、強酸などの煩雑な処理を必要とせずに製造し得る人工生体材料及びその製造方法を提供することを課題とする。
【０００５】
【課題を解決するための手段】
本発明者等は鋭意努力した結果、コロイダルシリカ粒子が、研磨、熱、アルカリ、強酸などの処理をせずにチタン表面に効率的に付着し、その結果得られる人工生体材料が優れた石灰化促進能を有することを見出し、本発明を完成させた。
即ち、本発明の人工生体材料は、材料表面にコロイダルシリカ粒子を有することを特徴とする。本発明を以下に述べる。
発明の第一観点は、生体内に埋め込まれて使用される材料であって、その材料、好ましくはチタン又はチタン合金の表面にコロイダルシリカ粒子、好ましくは平均粒径が４〜１００ｎｍであるコロイダルシリカ粒子を付着させた人工生体材料である。
発明の第二観点は、第一観点に記載された人工生体材料からなる、歯科治療に使用される歯欠損部用充填材料である。
発明の第三観点は、第一観点に記載された人工生体材料からなる、整形外科治療に使用される人工骨又は人工関節である。
発明の第四観点は、材料を、コロイダルシリカ粒子の懸濁液に、好ましくはシリカ濃度が０．０１〜４０質量％であるコロイダルシリカ粒子の懸濁液に接触させ、温度１〜１１５℃にて乾燥させることからなる第一観点に記載された人工生体材料の製造方法である。
【０００６】
本発明で使用されるコロイダルシリカ粒子は、４〜１００ｎｍの平均粒径を有するシリカ粒子である。
【０００７】
一般にコロイダルシリカと称される、コロイダルシリカ粒子の安定な懸濁液が販売されている。ここではコロイダルシリカ粒子は、市販のコロイダルシリカを用いるとコロイダルシリカ粒子のパウダーを分散させずに使用できて好ましい。
【０００８】
コロイダルシリカは、平均粒径により任意に選択することができる。また、安定な水性懸濁液の形態として、ナトリウム安定型コロイダルシリカ、アンモニア安定型コロイダルシリカ、酸性安定型コロイダルシリカが知られている。
【０００９】
例えば、ナトリウム安定型コロイダルシリカとしては、スノーテックス（登録商標） ＸＳ（日産化学工業（株）製）：平均粒径４ｎｍ、スノーテックス（登録商標） Ｓ（日産化学工業（株）製）：平均粒径９ｎｍ、スノーテックス（登録商標） ３０（日産化学工業（株）製）：平均粒径１２ｎｍ、スノーテックス（登録商標） ５０（日産化学工業（株）製）：平均粒径２１ｎｍ、スノーテックス（登録商標） ＸＬ（日産化学工業（株）製）：平均粒径４５ｎｍ、スノーテックス（登録商標） ＹＬ（日産化学工業（株）製）：平均粒径６５ｎｍ、スノーテックス（登録商標） ＺＬ（日産化学工業（株）製）：平均粒径８５ｎｍなどが挙げられる。
【００１０】
同じく、アンモニア安定型コロイダルシリカとしては、スノーテックス（登録商標） ＮＸＳ（日産化学工業（株）製）：平均粒径４ｎｍ、スノーテックス（登録商標） ＮＳ（日産化学工業（株）製）：平均粒径９ｎｍ、スノーテックス（登録商標） Ｎ（日産化学工業（株）製）：平均粒径１２ｎｍ、スノーテックス（登録商標） Ｎ−４０（日産化学工業（株）製）：平均粒径２１ｎｍなどが挙げられる。
【００１１】
そして、酸性安定型コロイダルシリカとしては、スノーテックス（登録商標）ＯＸＳ（日産化学工業（株）製）：平均粒径４ｎｍ、スノーテックス（登録商標） ＯＳ（日産化学工業（株）製）：平均粒径９ｎｍ、スノーテックス（登録商標） Ｏ（日産化学工業（株）製）：平均粒径１２ｎｍ、スノーテックス（登録商標） Ｏ−４０（日産化学工業（株）製）：平均粒径２１ｎｍなどが挙げられる。
【００１２】
また、コロイダルシリカの安定な有機溶媒の懸濁液もあり使用することができる。有機溶媒型コロイダルシリカとしては、メタノール溶媒型としてＭＡ−ＳＴ（日産化学工業（株）製）：平均粒径１２ｎｍ、イソプロパノール溶媒型ＩＰＡ−ＳＴ（日産化学工業（株）製）：平均粒径１２ｎｍなどが挙げられる。
【００１３】
このコロイダルシリカ粒子（コロイダルシリカ）の平均粒径は、通常窒素吸着法により測定された比表面積より球状粒子に換算して得られる、窒素吸着法粒子径が採用されている。その平均粒径（Ｄｎｍ）は、比表面積Ｓｍ2／ｇと真比重ｄｇ／ｃｍ3とから、Ｄ＝６０００／（Ｓ×ｄ）の式によって与えられる。
【００１４】
コロイダルシリカ粒子の平均粒径としては、４〜１００ｎｍである。コロイダルシリカ粒子の粒子径が小さい方がより付着力が強くなり好ましい。よって、好ましくは４〜５０ｎｍ、より好ましくは４〜２０ｎｍである。
【００１５】
本発明における生体内に埋め込まれて使用される材料としては、アルミナ、ジルコニア、ステンレス合金、Ｎｉ−Ｃｒ合金、Ｃｏ−Ｃｒ合金、チタン、チタン合金などから選択することができる。なかでもチタン又はチタン合金が好ましい。
チタン合金としては、チタン（Ｔｉ）を主成分とするが、Ａｌ、Ｓｎ、Ｚｒ、Ｍｏ、Ｎｉ、Ｐｄ、Ｔａ、Ｎｂ、Ｖ、Ｐｔなどを添加した合金を使用することができる。好ましくはＴｉ−６Ａｌ−４Ｖ合金が挙げられる。
【００１６】
次に、人工生体材料の製造方法について述べる。
形状として、線状、網状、斑点状、もしくはこれらの形状を組み合わせた種々のパターンを有する材料を用意する。
【００１７】
次いで、材料をコロイダルシリカ粒子の懸濁液（コロイダルシリカ）に接触させる。ここで、接触方法として、浸漬、塗布など公知の方法を用いることができる。
【００１８】
高濃度のコロイダルシリカでの接触処理後は、適宜水洗などで、過剰の付着コロイダルシリカ粒子を除くことが好ましい。
【００１９】
ここで、コロイダルシリカのシリカ（ＳｉＯ2）濃度としては、１０〜４０質量％のものが市販品より入手することができる。コロイダルシリカのシリカ濃度は、０．０１〜４０質量％に濃度調製して使用することができる。
【００２０】
ここで、接触処理後における水洗工程を入れる場合は、シリカ濃度１０〜４０質量％であり、接触処理後における水洗工程を除くことを希望する場合は、シリカ濃度０．０１〜１０質量％が挙げられる。
【００２１】
接触処理後の材料は、温度１〜１１５℃にて乾燥させることにより、容易に材料表面にコロイダルシリカ粒子を付着させることができる。乾燥においては、コロイダルシリカ粒子の付着水が除去される。
【００２２】
大気中での乾燥では、日本薬局方で室温と称される温度１〜３０℃、同様に常温と称される温度１５〜２５℃で行うことができる。恒温乾燥機を用いる乾燥では、３０〜１１５℃で行うことができる。
【００２３】
かように得られた本発明の人工生体材料は、歯科治療における歯欠損部用充填材料として、又は整形外科治療における人工骨又は人工関節器具として有益である。
【００２４】
【実施例】
実施例
ＪＩＳ２種純チタン板（１０ｍｍ×１０ｍｍ×１ｍｍ）を３５ｍｍ径のプラスティックシャーレに入れコロイダルシリカ粒子の懸濁液（シリカ濃度２０質量％：スノーテックス（登録商標） Ｏ、日産化学工業（株）製）２ｍｌを加えた。２４時間後、チタン板を取り出して水洗後乾燥させて本発明の人工生体材料となした。
比較例１〜４
コロイダルシリカにより処理されたチタン板（本発明の人工生体材料）の比較として、ＪＩＳ２種純チタン板（１０ｍｍ×１０ｍｍ×１ｍｍ）を、無処理（比較例１）、耐水研磨紙（＃８００）（比較例２）及びアルミナ研磨紙（＃８００）（比較例３）の自動研磨装置による約２０分の研磨、並びに６０℃で２４時間の５Ｍ水酸化ナトリウム（ＮａＯＨ）水溶液処理（アルカリ処理）（比較例４）して比較例１ないし４の人工生体材料をそれぞれ作製した。
【００２５】
試験例１：石灰化量の定量試験
上述の実施例で得られた本発明の人工生体材料を３５ｍｍ径のプラスティックシャーレに入れ、これに０．５μＣｉ／ｍｌの45Ｃａを含有したＭＥＭ液（シグマ・アルドリッチ社製）２ｍｌを加えて３７℃、５％ＣＯ2条件下に置いた。７日後、人工生体材料を取り出して温度２０℃で乾燥後、表面の45Ｃａ量を測定した。その結果を図１に示す。
一方で、比較例１ないし４の人工生体材料を３５ｍｍ径のプラスティックシャーレにそれぞれ入れ、０．５μＣｉ／ｍｌの45Ｃａを含有したＭＥＭ液（シグマ・アルドリッチ社製）２ｍｌを加えて３７℃、５％ＣＯ2条件下に置いた。７日後、人工生体材料を取り出して温度２０℃で乾燥後、表面の45Ｃａ量を測定した。その結果を図１に示す。
結 果
チタン板の無処理（比較例１）においては、石灰化が殆ど認められなかった。また、チタン板の耐水研磨紙による研磨（比較例２）、アルミナ研磨紙による研磨（比較例３）およびアルカリ処理（比較例４）により得られた人工生体材料においては石灰化は認められるものの、十分ではなかった。これに対して、チタン板のコロイダルシリカ処理により得られた本発明の人工生体材料（実施例）では、強力な石灰化作用が認められ、アルカリ処理のおよそ３倍のカルシウム形成がみられた。
【００２６】
試験例２：チタン表面粒子の電子顕微鏡観察および結合状態
ＪＩＳ ２種純チタン板（１０ｍｍ×１０ｍｍ×１ｍｍ）を３５ｍｍ径のプラスティックシャーレに入れコロイダルシリカ（シリカ濃度２０質量％：スノーテックス（登録商標） Ｏ、日産化学工業（株）製）２ｍｌを加えた。２４時間後、チタン板を取り出して水洗後乾燥させて本発明の人工生体材料となした後、該人工生体材料を３５ｍｍ径のプラスティックシャーレに入れ、これに０．５μＣｉ／ｍｌの45Ｃａを含有したＭＥＭ液（シグマ・アルドリッチ社製）２ｍｌを加えて３７℃、５％ＣＯ2条件下で培養した。７日後、人工生体材料を取り出して温度２０℃で乾燥させ、その表面を電解放射型走査型電子顕微鏡（ＦＥ−ＳＥＭ）にて観察した。その撮影写真を図２に示す。次に、コロイダルシリカ粒子のチタン板への結合状態を確認する為に、人工生体材料を超音波洗浄処理した後、ＦＥ−ＳＥＭで観察した。
（１）チタン表面粒子の電子顕微鏡観察
コロイダルシリカ処理後のチタン表層には、コロイダルシリカ粒子の表面付着が認められた。さらに、大きさ数μｍ程度の顆粒状石灰化物が高密度に認められた（図２参照。）。
（２）チタン表面粒子の結合状態
このチタン表層に結合したコロイダルシリカ粒子は、超音波洗浄処理によっても剥がれるなどの影響は見られなかった。
【００２７】
試験例３：コロイダルシリカによる石灰化作用の処理時間の検討
ＪＩＳ２種純チタン板（１０ｍｍ×１０ｍｍ×１ｍｍ）を３５ｍｍ径のプラスティックシャーレに入れコロイダルシリカ（シリカ濃度２０質量％：スノーテックス（登録商標） Ｏ、日産化学工業（株）製）２ｍｌを加えた。６時間後及び２４時間後においてそれぞれ、チタン板を取り出して水洗後乾燥させ、０．５μＣｉ／ｍｌの45Ｃａを含有したＭＥＭ液（シグマ・アルドリッチ社製）２ｍｌを加えて３７℃、５％ＣＯ2条件下で培養した。２４時間後、チタン板を取り出して温度２０℃で乾燥後、その表面の45Ｃａ量を測定した。結果を図３に示す。
図３から、チタン板をコロイダルシリカにより６時間の短時間処理をしても、２４時間の処理をしたと同様の石灰化効果が認められた（図３参照。）。
【００２８】
【発明の効果】
本発明の人工生体材料は、生体内に埋没すると速やかにリン酸カルシウムの付着が起こる。ここでチタン板等へのコロイダルシリカ粒子の結合様式が付着によるため、従来のシリカゲル被覆層と比較して、骨組織との結合時にずれや剥離などが生じず、強固な生体融和が起こる。
よって、本発明の人工生体材料は、骨組織と短期間でかつ再現性よく結合することができるため、患者の負担を軽減する人工骨、人工関節、人工歯根等の人工生体材料として有用である。また、本発明の方法によれば、これらの人工生体材料を容易に作製することができる。
【図面の簡単な説明】
【図１】各々、無処理、耐水研磨紙、アルミナ研磨紙、アルカリ処理及びコロイダルシリカ処理されたチタン表面に付着したカルシウム量を示したグラフである。
【図２】コロイダルシリカが付着され、及び石灰化物が形成されたチタン表面を電子顕微鏡にて撮影した写真である。
【図３】コロイダルシリカによる処理を６時間及び２４時間行った後のチタン板に付着したカルシウム量を示したグラフである。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an artificial biomaterial (implant material) used by being implanted in a living body.
More specifically, the present invention relates to a colloidal silica particle-attached artificial biomaterial useful as an artificial biomaterial such as an artificial bone, an artificial joint, or an artificial tooth root, and a method for producing the same.
[0002]
[Prior art]
Conventionally, titanium artificial biomaterials have been used to replace bone defects. Titanium is known to have good affinity with bone tissue because calcium phosphate is formed on its surface (hereinafter referred to as calcification) in the human body.
As means for promoting calcification, alkali treatment of the titanium metal surface is known. There is also a method of polishing the titanium metal surface with sandpaper. The cause of the promotion is considered to be that calcification is promoted by silicon (Si) moving to the titanium surface layer and forming dense crystals. On the other hand, it is known that calcification is promoted by treating a silicon or titanium alkoxide with a strong acid to form a silica gel film layer on the titanium surface, and an improved method has been proposed (for example, See Patent Documents 1 to 4.)
However, in this treatment, since the high-temperature heating (400 to 1000 ° C.) treatment is performed in the formation of the silica gel coating layer, shrinkage and peeling of the silica gel coating layer are promoted. Therefore, there is a problem that the calcification ability becomes weak, the reproducibility is poor, and the process becomes complicated.
[0003]
[Patent Document 1]
JP-A-10-052484 (Claims and Detailed Description of the Invention)
[Patent Document 2]
Japanese Patent Laid-Open No. 10-052483 (Claims, Detailed Description of the Invention)
[Patent Document 3]
Japanese Unexamined Patent Publication No. 06-169981 (Claims, Detailed Description of the Invention)
[Patent Document 4]
JP 06-023030 A (Claims, Detailed Description of the Invention)
[0004]
[Problems to be solved by the invention]
An object of the present invention is to provide an artificial biomaterial that is excellent in calcification ability and can be manufactured without requiring complicated treatments such as polishing, heat, alkali, strong acid and the like on the titanium surface, and a method for manufacturing the same. And
[0005]
[Means for Solving the Problems]
As a result of diligent efforts, the present inventors have successfully colloidal silica particles adhered to the titanium surface without any treatment such as polishing, heat, alkali, strong acid, and the resulting artificial biomaterial has excellent calcification The present invention was completed by finding that it has a promoting ability.
That is, the artificial biomaterial of the present invention is characterized by having colloidal silica particles on the material surface. The present invention is described below.
A first aspect of the invention is a material used by being implanted in a living body, and preferably colloidal silica particles, preferably an average particle diameter of 4 to 100 nm on the surface of the material, preferably titanium or a titanium alloy. It is an artificial biomaterial with particles attached.
A second aspect of the invention is a filling material for a tooth defect portion used for dental treatment, which is made of the artificial biomaterial described in the first aspect.
A third aspect of the invention is an artificial bone or joint used for orthopedic treatment, comprising the artificial biomaterial described in the first aspect.
According to a fourth aspect of the invention, the material is brought into contact with a suspension of colloidal silica particles, preferably a suspension of colloidal silica particles having a silica concentration of 0.01 to 40% by mass, and the temperature is set to 1 to 115 ° C. It is a manufacturing method of the artificial biomaterial described in the first aspect consisting of drying.
[0006]
The colloidal silica particles used in the present invention are silica particles having an average particle diameter of 4 to 100 nm.
[0007]
A stable suspension of colloidal silica particles, commonly referred to as colloidal silica, is on the market. Here, as the colloidal silica particles, it is preferable to use commercially available colloidal silica because the colloidal silica particles can be used without being dispersed.
[0008]
Colloidal silica can be arbitrarily selected depending on the average particle diameter. Further, sodium stable colloidal silica, ammonia stable colloidal silica, and acidic stable colloidal silica are known as stable aqueous suspension forms.
[0009]
For example, as sodium-stable colloidal silica, Snowtex (registered trademark) XS (manufactured by Nissan Chemical Industries, Ltd.): average particle size 4 nm, Snowtex (registered trademark) S (manufactured by Nissan Chemical Industries, Ltd.): average Particle size 9 nm, Snowtex (registered trademark) 30 (Nissan Chemical Industry Co., Ltd.): Average particle size 12 nm, Snowtex (registered trademark) 50 (Nissan Chemical Industry Co., Ltd.): Average particle size 21 nm, Snowtex (Registered trademark) XL (manufactured by Nissan Chemical Industries, Ltd.): average particle size 45 nm, Snowtex (registered trademark) YL (manufactured by Nissan Chemical Industries, Ltd.): average particle size 65 nm, Snowtex (registered trademark) ZL ( (Manufactured by Nissan Chemical Industries, Ltd.): An average particle diameter of 85 nm and the like can be mentioned.
[0010]
Similarly, as the ammonia stable colloidal silica, Snowtex (registered trademark) NXS (manufactured by Nissan Chemical Industries, Ltd.): average particle size 4 nm, Snowtex (registered trademark) NS (manufactured by Nissan Chemical Industries, Ltd.): average Particle size 9 nm, Snowtex (registered trademark) N (manufactured by Nissan Chemical Industries, Ltd.): Average particle size 12 nm, Snowtex (registered trademark) N-40 (manufactured by Nissan Chemical Industries, Ltd.): average particle size 21 nm, etc. Is mentioned.
[0011]
As the acid-stable colloidal silica, Snowtex (registered trademark) OXS (manufactured by Nissan Chemical Industries, Ltd.): average particle size 4 nm, Snowtex (registered trademark) OS (manufactured by Nissan Chemical Industries, Ltd.): average Particle size 9 nm, Snowtex (registered trademark) O (Nissan Chemical Industry Co., Ltd.): Average particle size 12 nm, Snowtex (registered trademark) O-40 (Nissan Chemical Industry Co., Ltd.): Average particle size 21 nm, etc. Is mentioned.
[0012]
In addition, a suspension of colloidal silica in a stable organic solvent can be used. As the organic solvent type colloidal silica, MA-ST (manufactured by Nissan Chemical Industries, Ltd.): average particle size 12 nm, isopropanol solvent type IPA-ST (manufactured by Nissan Chemical Industries, Ltd.): average particle size 12 nm as methanol solvent type Etc.
[0013]
As the average particle diameter of the colloidal silica particles (colloidal silica), a nitrogen adsorption method particle diameter obtained by converting to a spherical particle from a specific surface area usually measured by a nitrogen adsorption method is adopted. The average particle diameter (Dnm) is given by the formula D = 6000 / (S × d) from the specific surface area Sm 2 / g and the true specific gravity dg / cm 3 .
[0014]
The average particle size of the colloidal silica particles is 4 to 100 nm. It is preferable that the colloidal silica particles have a smaller particle size because the adhesion is stronger. Therefore, it is preferably 4 to 50 nm, more preferably 4 to 20 nm.
[0015]
The material used by being implanted in the living body in the present invention can be selected from alumina, zirconia, stainless alloy, Ni—Cr alloy, Co—Cr alloy, titanium, titanium alloy, and the like. Of these, titanium or a titanium alloy is preferable.
As a titanium alloy, although titanium (Ti) is a main component, an alloy to which Al, Sn, Zr, Mo, Ni, Pd, Ta, Nb, V, Pt, or the like is added can be used. A Ti-6Al-4V alloy is preferable.
[0016]
Next, a method for manufacturing an artificial biomaterial will be described.
As the shape, materials having a linear shape, a net shape, a spot shape, or various patterns obtained by combining these shapes are prepared.
[0017]
The material is then contacted with a suspension of colloidal silica particles (colloidal silica). Here, a known method such as dipping or coating can be used as the contact method.
[0018]
After the contact treatment with high-concentration colloidal silica, it is preferable to remove excess adhered colloidal silica particles by washing with water as appropriate.
[0019]
Here, the silica (SiO 2) concentration of the colloidal silica can be obtained from commercial products include the 10 to 40% by weight. The silica concentration of colloidal silica can be adjusted to 0.01 to 40% by mass and used.
[0020]
Here, when the water washing step after the contact treatment is added, the silica concentration is 10 to 40% by mass, and when it is desired to exclude the water washing step after the contact treatment, the silica concentration is 0.01 to 10% by mass. It is done.
[0021]
By drying the material after the contact treatment at a temperature of 1 to 115 ° C., the colloidal silica particles can be easily attached to the material surface. In drying, the adhering water of the colloidal silica particles is removed.
[0022]
Drying in the air can be performed at a temperature of 1 to 30 ° C., which is called room temperature in the Japanese Pharmacopoeia, and at a temperature of 15 to 25 ° C. which is also called normal temperature. Drying using a thermostatic dryer can be performed at 30 to 115 ° C.
[0023]
The artificial biomaterial of the present invention thus obtained is useful as a dental defect filling material in dental treatment or as an artificial bone or artificial joint device in orthopedic treatment.
[0024]
【Example】
Example JIS type 2 pure titanium plate (10 mm × 10 mm × 1 mm) was placed in a 35 mm diameter plastic petri dish and a suspension of colloidal silica particles (silica concentration 20% by mass: Snowtex (registered trademark) O, Nissan Chemical Industries, Ltd. 2 ml) was added. After 24 hours, the titanium plate was taken out, washed with water and dried to obtain the artificial biomaterial of the present invention.
Comparative Examples 1-4
As a comparison of a titanium plate treated with colloidal silica (artificial biomaterial of the present invention), a JIS type 2 pure titanium plate (10 mm × 10 mm × 1 mm) was not treated (Comparative Example 1), water-resistant abrasive paper (# 800) ( Comparative Example 2) and alumina polishing paper (# 800) (Comparative Example 3) polished by an automatic polishing apparatus for about 20 minutes, and treated with 5M sodium hydroxide (NaOH) aqueous solution (alkali treatment) at 60 ° C. for 24 hours (comparison) Example 4) and artificial biomaterials of Comparative Examples 1 to 4 were produced.
[0025]
Test Example 1: Quantitative test of calcification amount The artificial biomaterial of the present invention obtained in the above-mentioned Examples was placed in a 35 mm diameter plastic petri dish, and contained 0.5 μCi / ml of 45 Ca. 2 ml of MEM solution (manufactured by Sigma-Aldrich) was added and placed under conditions of 37 ° C. and 5% CO 2 . Seven days later, the artificial biomaterial was taken out and dried at a temperature of 20 ° C., and the amount of 45 Ca on the surface was measured. The result is shown in FIG.
On the other hand, each of the artificial biomaterials of Comparative Examples 1 to 4 was put into a 35 mm diameter plastic petri dish, and 2 ml of MEM solution (manufactured by Sigma-Aldrich) containing 0.5 μCi / ml of 45 Ca was added at 37 ° C., 5 Placed in% CO 2 conditions. Seven days later, the artificial biomaterial was taken out and dried at a temperature of 20 ° C., and the amount of 45 Ca on the surface was measured. The result is shown in FIG.
Results Almost no calcification was observed in the untreated titanium plate (Comparative Example 1). In addition, although calcification is observed in the artificial biomaterial obtained by polishing the titanium plate with water-resistant polishing paper (Comparative Example 2), polishing with alumina polishing paper (Comparative Example 3) and alkali treatment (Comparative Example 4), It was not enough. On the other hand, in the artificial biomaterial (Example) of the present invention obtained by the colloidal silica treatment of the titanium plate, a strong calcification action was observed, and calcium formation about three times that of the alkali treatment was observed.
[0026]
Test Example 2: Electron microscope observation and bonding state of titanium surface particles JIS type 2 pure titanium plate (10 mm × 10 mm × 1 mm) was placed in a 35 mm diameter plastic petri dish and colloidal silica (silica concentration 20 mass%: Snowtex (registered trademark)) O, 2 ml of Nissan Chemical Industries, Ltd.) was added. After 24 hours, the titanium plate was taken out, washed with water and dried to obtain the artificial biomaterial of the present invention. Then, the artificial biomaterial was put into a 35 mm diameter plastic petri dish, which contained 0.5 μCi / ml of 45 Ca. 2 ml of the prepared MEM solution (manufactured by Sigma-Aldrich) was added and cultured under conditions of 37 ° C. and 5% CO 2 . Seven days later, the artificial biomaterial was taken out and dried at a temperature of 20 ° C., and the surface thereof was observed with an electrolytic emission scanning electron microscope (FE-SEM). The photograph taken is shown in FIG. Next, in order to confirm the bonding state of the colloidal silica particles to the titanium plate, the artificial biomaterial was subjected to ultrasonic cleaning treatment and then observed with an FE-SEM.
(1) Electron microscope observation of titanium surface particles The surface adhesion of colloidal silica particles was observed on the titanium surface layer after the treatment with colloidal silica. Furthermore, granular calcifications having a size of several μm were observed at a high density (see FIG. 2).
(2) Bonding state of titanium surface particles The colloidal silica particles bonded to the titanium surface layer were not affected by peeling off even by ultrasonic cleaning treatment.
[0027]
Test Example 3: Examination of treatment time for calcification by colloidal silica JIS type 2 pure titanium plate (10 mm × 10 mm × 1 mm) was placed in a 35 mm diameter plastic petri dish and colloidal silica (silica concentration 20% by mass: Snowtex (registered trademark)) O, 2 ml of Nissan Chemical Industries, Ltd.) was added. After 6 hours and 24 hours, respectively, the titanium plate was taken out, washed with water and dried, and 2 ml of MEM solution (manufactured by Sigma-Aldrich) containing 0.5 μCi / ml of 45 Ca was added thereto at 37 ° C., 5% CO Cultured under 2 conditions. After 24 hours, the titanium plate was taken out and dried at a temperature of 20 ° C., and the amount of 45 Ca on the surface was measured. The results are shown in FIG.
From FIG. 3, even if the titanium plate was treated with colloidal silica for a short time of 6 hours, the same calcification effect as that of the treatment for 24 hours was observed (see FIG. 3).
[0028]
【The invention's effect】
When the artificial biomaterial of the present invention is embedded in a living body, calcium phosphate adheres quickly. Here, since the bonding mode of the colloidal silica particles to the titanium plate or the like is due to adhesion, compared to the conventional silica gel coating layer, there is no displacement or peeling at the time of bonding with the bone tissue, and strong biocompatibility occurs.
Therefore, since the artificial biomaterial of the present invention can be combined with bone tissue in a short period of time and with high reproducibility, it is useful as an artificial biomaterial such as an artificial bone, an artificial joint, or an artificial tooth root that reduces the burden on the patient. . Further, according to the method of the present invention, these artificial biomaterials can be easily produced.
[Brief description of the drawings]
BRIEF DESCRIPTION OF DRAWINGS FIG. 1 is a graph showing the amount of calcium adhering to a titanium surface treated with no treatment, water-resistant abrasive paper, alumina abrasive paper, alkali treatment and colloidal silica.
FIG. 2 is a photograph taken with an electron microscope of a titanium surface on which colloidal silica is adhered and calcified substances are formed.
FIG. 3 is a graph showing the amount of calcium adhering to a titanium plate after treatment with colloidal silica for 6 hours and 24 hours.
Claims (6)
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| KR100876529B1 (en) * | 2004-09-15 | 2008-12-31 | 주식회사 엘지화학 | Film or building exterior material using self-cleaning coating composition and method for producing same |
| JPWO2007043149A1 (en) * | 2005-10-05 | 2009-04-16 | 株式会社ホムズ技研 | Implant for osteosynthesis and method for producing the same |
| CN102131489A (en) | 2008-08-20 | 2011-07-20 | 株式会社器官再生工学 | Method for restoring missing tooth and method for producing restorative material |
| JP5892547B2 (en) * | 2012-05-31 | 2016-03-23 | カーリットホールディングス株式会社 | Conductive polymer dispersion for production of solid electrolytic capacitor and solid electrolytic capacitor produced using the same |
| CN105105859A (en) * | 2015-09-01 | 2015-12-02 | 深圳市义和平有限公司 | Improved artificial dental implant with porous lamina and production method of improved artificial dental implant |
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| JPH10512227A (en) * | 1995-01-13 | 1998-11-24 | ブリンク，マリア | New bioactive glasses and their use |
| WO2001015751A1 (en) * | 1999-09-01 | 2001-03-08 | Bioxid Oy | Novel multilayered material bearing a biologically active agent and the preparation thereof |
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