JP2002327079A - Titanium oxide/organic polymer composite suitable as artificial bone and the like - Google Patents
Titanium oxide/organic polymer composite suitable as artificial bone and the likeInfo
- Publication number
- JP2002327079A JP2002327079A JP2001135160A JP2001135160A JP2002327079A JP 2002327079 A JP2002327079 A JP 2002327079A JP 2001135160 A JP2001135160 A JP 2001135160A JP 2001135160 A JP2001135160 A JP 2001135160A JP 2002327079 A JP2002327079 A JP 2002327079A
- Authority
- JP
- Japan
- Prior art keywords
- titanium oxide
- organic polymer
- apatite
- resin
- polymer composite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- Treatments Of Macromolecular Shaped Articles (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Materials For Medical Uses (AREA)
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、少なくともアナタ
ーゼ型二酸化チタン微粒子と硬化性あるいは熱可塑性有
機高分子との複合材料から得られる、擬似体液などのア
パタイトに対して過飽和な水溶液中もしくは体内でアパ
タイト形成能を有する骨置換用あるいは骨修復用アナタ
ーゼ型酸化チタン・有機高分子複合体およびアパタイト
が表面に形成された骨置換用あるいは骨修復用アナター
ゼ型酸化チタン・有機高分子複合体に関する。The present invention relates to apatite in an aqueous solution or a body supersaturated with respect to apatite, such as a simulated body fluid, obtained from a composite material of at least anatase type titanium dioxide fine particles and a curable or thermoplastic organic polymer. The present invention relates to an anatase-type titanium oxide / organic polymer composite for bone replacement or bone repair having a forming ability and an anatase-type titanium oxide / organic polymer composite for bone replacement or bone repair having apatite formed on the surface.
【０００２】[0002]
【従来の技術】天然の骨は、有機質コラーゲン繊維がア
パタイト結晶を繋ぎ合わせて構成された３次元複合体で
ある。このような構造は、有機高分子のコラーゲン繊維
上に無機質のアパタイト微結晶が規則正しく析出したも
のが３次元的に織・編み上げられることにより形成され
ている。有機質コラーゲン繊維は、アパタイトに対して
相補的な補強作用をし、骨に外圧が加わったときの変形
を可能にする（可撓性が付与される）。このような機械
的構造を、アパタイトで被覆された有機高分子繊維から
３次元的に作り上げることができれば、得られた材料
は、天然の骨と同様の骨結合能および機械的特性を持つ
ことから、人工骨用アパタイト・高分子複合体として有
用である。そして、このような、観点に基づく新しい人
工骨の開発が盛んに行われている。（例えばMasami Tan
ahashiら、J. Am. Ceram. Soc. １９９４年第７７巻２
８０５頁、Yasuo Shikinamiら、Biomaterials １９９８
年第１９巻６１７頁）。2. Description of the Related Art Natural bone is a three-dimensional complex composed of organic collagen fibers joined with apatite crystals. Such a structure is formed by three-dimensionally weaving and knitting inorganic apatite microcrystals regularly deposited on an organic polymer collagen fiber. The organic collagen fibers have a complementary reinforcing effect on apatite, and enable deformation (providing flexibility) when bone is subjected to external pressure. If such a mechanical structure can be made three-dimensionally from organic polymer fibers coated with apatite, the resulting material will have the same osteointegration and mechanical properties as natural bone. It is useful as an apatite-polymer composite for artificial bone. And development of such a new artificial bone based on a viewpoint is actively performed. (For example, Masami Tan
ahashi et al., J. Am. Ceram. Soc.
805, Yasuo Shikinami et al., Biomaterials 1998.
19, 617).
【０００３】特開平１０−２４４１６６号公報には、多
孔質リン酸カルシウム膜をコートした酸化チタン、特に
アナターゼ結晶型の酸化チタンを、擬似体液中に前記酸
化チタンを表面に有する基材を浸漬することにより製造
すること、およびこうして得られた材料を有機繊維やプ
ラスチックに練り込んだものは、前記酸化チタンの光触
媒作用により前記有機繊維やプラスチックの劣化をもた
らすことがないことが記載されているが、前記酸化チタ
ンをそのまま有機繊維やプラスチックに練り込んだもの
が、擬似体液などのアパタイトに対して過飽和な水溶液
中で該表面にアパタイトを生成することについては、全
く記載されていない。JP-A-10-244166 discloses that a porous calcium phosphate membrane-coated titanium oxide, particularly titanium oxide of anatase crystal type, is immersed in a simulated body fluid by immersing a substrate having the titanium oxide on the surface. It is described that the produced and kneaded material thus obtained in organic fibers and plastics do not cause deterioration of the organic fibers and plastics due to the photocatalytic action of the titanium oxide. There is no description about producing titanium apatite on an organic fiber or plastic as it is kneaded in an aqueous solution supersaturated with apatite such as a simulated body fluid.
【０００４】A C S Symp Ser(Am Chem Soc)，No.585,P6
-18、には、ポリプロピレン（ＰＰ）およびチタンブト
キシドを溶融押し出した後、加水分解することによりサ
ブミクロン（ナノ）サイズの二酸化チタンを含む無機−
有機複合材料を作ったことが、また、Polym Mater Sci
Eng,Vol.70,P224-225,1994、には、ＰＰ、酸化チタン、
核剤およびカップリング剤から、骨に類似した合成材料
を製造したことが、記載されているが、該材料が擬似体
液などのアパタイトに対して過飽和な水溶液中において
アパタイト形成能を有するかどうかの考察もされていな
いし、骨修復材料として有用であることを示唆する記載
もない。すなわち、有機高分子とアナターゼ微粒子との
配合物から、擬似体液などのアパタイトに対して過飽和
な水溶液中においてアパタイト形成能を持つ無機−有機
複合体を得るという発想は全く新しいものである。[0004] ACS Symp Ser (Am Chem Soc), No. 585, P6
-18, an inorganic material containing titanium dioxide having a submicron (nano) size by melting and extruding polypropylene (PP) and titanium butoxide.
The fact that organic composites were made
Eng, Vol. 70, P224-225, 1994, has PP, titanium oxide,
It has been described that a synthetic material similar to bone was produced from a nucleating agent and a coupling agent, but whether the material has apatite-forming ability in an aqueous solution supersaturated with respect to apatite such as a simulated body fluid. There is no discussion or suggestion that it is useful as a bone repair material. That is, the idea of obtaining an inorganic-organic composite having apatite-forming ability in an aqueous solution supersaturated with apatite such as a simulated body fluid from a blend of an organic polymer and anatase fine particles is completely new.
【０００５】[0005]
【発明が解決しようとする課題】本願発明の課題は、前
記発想に基づいて、少なくとも有機高分子およびアナタ
ーゼ型二酸化チタン微粒子との配合物からなり、擬似体
液などのアパタイトに対して過飽和な水溶液中において
アパタイト形成能を持つアナターゼ型二酸化チタン微粒
子・有機高分子複合体、および該複合体表面にアパタイ
トを形成させたアナターゼ型二酸化チタン微粒子・有機
高分子複合体を提供することである。前記課題を解決す
るためには、二酸化チタンは、前記従来技術においても
言及している様に、有機物の分解反応において触媒作用
をするという有用な機能も、本発明のような用途におい
ては不都合をもたらすという厄介な問題があり、前記不
都合を起こさない好ましい有機高分子およびアナターゼ
型二酸化チタン微粒子の組み合わせを見出すことが重要
であり、これらを含めて、前記課題を解決できる無機−
有機複合体を、材料、製法、構造などの種々の面から検
討した。SUMMARY OF THE INVENTION An object of the present invention, based on the above-mentioned idea, is to prepare a mixture of at least an organic polymer and fine particles of anatase type titanium dioxide, which is supersaturated with an apatite such as a simulated body fluid. The present invention provides an anatase type titanium dioxide fine particle / organic polymer composite having apatite forming ability and an anatase type titanium dioxide fine particle / organic polymer composite having apatite formed on the surface of the composite. In order to solve the above-mentioned problem, titanium dioxide has a useful function of catalyzing a decomposition reaction of an organic substance, as mentioned in the above-mentioned prior art. It is important to find a combination of a preferred organic polymer and anatase-type titanium dioxide fine particles that does not cause the above-mentioned disadvantages.
Organic composites were studied from various aspects such as materials, manufacturing methods, and structures.
【０００６】[0006]
【課題を解決するための手段】本発明は、少なくともア
ナターゼ型二酸化チタン微粒子または該微粒子の前駆体
化合物と硬化性または熱可塑性樹脂とからなる配合物を
用いて成形した、または該成形物から切り出された物ま
たは該成形物を組織化した複合材料を、機械的研磨また
は／および化学的処理により複合材料の表面に擬似体液
などのアパタイトに対して過飽和な水溶液中もしくは体
内においてアパタイトを形成する能力を持つアナターゼ
型二酸化チタン微粒子を露出させて得られる酸化チタン
・有機高分子複合体である。好ましくは、硬化性または
熱可塑性樹脂がエポキシ系樹脂、飽和または不飽和ポリ
エステル系樹脂、ポリアミド系樹脂、シリコーン樹脂、
ポリオレフィン系樹脂、ポリスチレン、アクリロニトリ
ル−ブタジエン−スチレン共重合体樹脂、アクリロニト
リル−スチレン共重合体樹脂、ポリカーボネート系樹
脂、ポリアセタールから選択される酸化チタン光触媒特
性による酸化・還元作用により実質的に劣化しない少な
くとも１種の樹脂であることを特徴とする前記酸化チタ
ン・有機高分子複合体であり、より好ましくは、硬化性
または熱可塑性樹脂がエポキシ系樹脂、飽和または不飽
和ポリエステル系樹脂、シリコーン樹脂、ポリエチレン
から選択される酸化チタン光触媒特性による酸化・還元
作用により実質的に劣化しない少なくとも１種の樹脂で
あることを特徴とする前記酸化チタン有機高分子複合体
である。また、前記成形物がブロック、シート、ファイ
バー、テープ、またはフィラメント状であり、切り出さ
れた物および組織化された物の形状がスライバー、ヤー
ン、不織布、２次元または３次元織編物である前記各酸
化チタン有機高分子複合体である。更に前記各酸化チタ
ン・有機高分子複合体の表面に擬似体液などのアパタイ
トに対して過飽和な水溶液中においてアパタイトを形成
させた人工骨および骨修復用の各酸化チタン−有機高分
子複合体である。SUMMARY OF THE INVENTION The present invention relates to a method for molding or cutting out a compound comprising at least a fine particle of anatase type titanium dioxide or a precursor compound of the fine particle and a curable or thermoplastic resin. Ability to form apatite in a supersaturated aqueous solution or apatite such as a simulated body fluid on the surface of a composite material by mechanical polishing or / and chemical treatment of a composite material obtained by assembling the molded product or the molded material. Is a titanium oxide-organic polymer composite obtained by exposing anatase type titanium dioxide fine particles having the following. Preferably, the curable or thermoplastic resin is an epoxy resin, a saturated or unsaturated polyester resin, a polyamide resin, a silicone resin,
At least one which is not substantially deteriorated by oxidation / reduction by photocatalytic properties of titanium oxide selected from polyolefin resin, polystyrene, acrylonitrile-butadiene-styrene copolymer resin, acrylonitrile-styrene copolymer resin, polycarbonate resin and polyacetal. The above-mentioned titanium oxide-organic polymer composite characterized by being a kind of resin, more preferably, the curable or thermoplastic resin is an epoxy resin, a saturated or unsaturated polyester resin, a silicone resin, or polyethylene. The above-mentioned titanium oxide-organic polymer composite, characterized in that it is at least one kind of resin that does not substantially deteriorate due to the oxidation / reduction action due to the selected titanium oxide photocatalytic properties. Further, each of the molded articles is a block, a sheet, a fiber, a tape, or a filament, and each of the cut and organized articles is a sliver, a yarn, a nonwoven fabric, a two-dimensional or three-dimensional woven or knitted article. It is a titanium oxide organic polymer composite. Further, each titanium oxide-organic polymer composite for artificial bone and bone repair in which apatite is formed in an aqueous solution supersaturated with respect to apatite such as a simulated body fluid on the surface of each titanium oxide-organic polymer composite. .
【０００７】[0007]
【本発明の実施の態様】本発明をより詳細に説明する。 Ａ．本発明の特徴をより詳細に説明する。本発明の人工
骨および骨修復用の各酸化チタン−有機高分子複合体
は、酸化チタンによる酸化・還元触媒作用により劣化し
難い硬化性樹脂とアナターゼ型酸化チタン微粒子とから
実質的になる。酸化チタン微粒子とは、１００μｍ〜１
０ｎｍの平均粒径を持つアナターゼ型酸化チタンを意味
する。球状粒子を用いると、充填密度を上げ、複合体の
アパタイト形成能と機械的強度を上げることができる。 Ｂ．本発明で使用する硬化性樹脂としては、不飽和ポリ
エステル、例えばマルトー製の硬組織標本包埋樹脂、ビ
スフェノールＡ型のエポキシ樹脂〔例えば、昭和高分子
（株）製、アラルダイド スタンダード 主剤〕、変性
シリコーン系湿気硬化型１液弾性接着剤〔セメダイン
（株）社製「セメダインスーパーＸ」（商品名）〕など
を挙げることができ、または熱可塑性樹脂としては、ポ
リアルキレンテレフタレート、例えばＰＥＴのような飽
和ポリエステル系樹脂、ポリオレフィン、例えばポリエ
チレンなどを挙げることができる。BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail. A. The features of the present invention will be described in more detail. The titanium oxide-organic polymer composite for artificial bone and bone repair of the present invention is substantially composed of a curable resin which is hardly deteriorated by oxidation / reduction catalysis by titanium oxide and anatase type titanium oxide fine particles. The titanium oxide fine particles are 100 μm to 1 μm.
Means anatase type titanium oxide having an average particle size of 0 nm. When spherical particles are used, the packing density can be increased, and the apatite-forming ability and mechanical strength of the composite can be increased. B. Examples of the curable resin used in the present invention include unsaturated polyester, for example, a hard tissue specimen embedding resin manufactured by Maltoux, an epoxy resin of bisphenol A type (for example, Araldide Standard main agent manufactured by Showa Polymer Co., Ltd.), modified silicone Moisture-curable one-component elastic adhesive [“Cedine Super X” (trade name) manufactured by Cemedine Co., Ltd.] or the like, or as the thermoplastic resin, a polyalkylene terephthalate, for example, a saturated resin such as PET. Examples include polyester-based resins and polyolefins such as polyethylene.
【０００８】Ｃ．本発明で使用するアナターゼ型二酸化
チタン微粒子としては、市販のものを使用できる。市販
のものとしては、硫酸法により得られた、石原産業株式
会社製の、平均粒径２００、１００、２０ｎｍのアナタ
ーゼ微粒子（以下、Ｔ２００、Ｔ１００、Ｔ２０と表記
する。）を好ましいものとして挙げることができる。ま
た、ゾル−ゲル法により微粒子を調整することもでき
る。該調製方法は、チタン酸テトライソプロピルの２−
プロパノール溶液に、撹拌下超純水を滴下し撹拌（室温
下、１５分間）後乾燥（７０℃で２４時間）し、これを
８０℃の温水で処理（２４時間）し、乾燥、粉砕するこ
とにより得られる（以下、ＴＳと表記する。）。これら
のアナターゼ型二酸化チタン微粒子表面の粉末Ｘ線回折
パターンおよびフーリエ変換赤外拡散反射分光スペクト
ルを図１および図２示す。微粒子表面のＴｉ−ＯＨの量
は、Ｔ２００、Ｔ１００、Ｔ２０、ＴＳの順に増加する
ことが分かった。また、アナターゼ型二酸化チタン微粒
子としては、文献Ｊ．Ａｍ．Ｃｅｒａｍ．Ｓｏｃ．、75
(6)1587-95(1992)に記載の球形の二酸化チタン粉末を、
３０℃〜１２０℃のｐＨ７．０以下の温水中で処理して
得たものは粒子が球状に近く、かつ粒度分布が狭いの
で、本発明の複合体、特に繊維状の複合体を得る場合に
おいて、充填率を上げることができるので好ましい。C. As the anatase type titanium dioxide fine particles used in the present invention, commercially available ones can be used. As a commercially available product, anatase fine particles having an average particle size of 200, 100, and 20 nm (hereinafter referred to as T200, T100, and T20) manufactured by Ishihara Sangyo Co., Ltd. obtained by a sulfuric acid method are preferred. Can be. Fine particles can also be prepared by a sol-gel method. The preparation method is based on 2-isopropyltetraisopropyl titanate.
Ultrapure water is dropped into the propanol solution with stirring, stirred (at room temperature, 15 minutes), dried (at 70 ° C. for 24 hours), treated with warm water at 80 ° C. (24 hours), dried and pulverized. (Hereinafter, referred to as TS). The powder X-ray diffraction pattern and the Fourier transform infrared diffuse reflection spectrum of the surface of these anatase type titanium dioxide fine particles are shown in FIG. 1 and FIG. It was found that the amount of Ti-OH on the surface of the fine particles increased in the order of T200, T100, T20, and TS. Further, as anatase type titanium dioxide fine particles, reference is made to J. Appl. Am. Ceram. Soc. , 75
(6) 1587-95 (1992) spherical titanium dioxide powder according to,
In the case of obtaining the composite of the present invention, particularly a fibrous composite, those obtained by treating in warm water having a pH of 7.0 or less at 30 ° C. to 120 ° C. have a particle shape close to a sphere and a narrow particle size distribution. , Since the filling rate can be increased.
【０００９】Ｄ，少なくともアナターゼ型二酸化チタン
微粒子または該微粒子の前駆体化合物と硬化性または熱
可塑性樹脂とからなる配合物を用いて成形物を製造する
工程としては、 １，硬化性または熱可塑性樹脂とアナターゼ型二酸化チ
タン微粒子または該微粒子の前駆体化合物とを混合した
後、該混合物を、成形型内で硬化または押出成形（加熱
溶融しても良い）させ成形する方法、 ２，溶剤を用いて均一分散液または溶液とし、該溶液を
成形型内に入れ溶媒を除去することによりまたは気体中
または凝固浴中に押出して成形する方法などがある。D, the step of producing a molded article using at least a compound comprising anatase type titanium dioxide fine particles or a precursor compound of the fine particles and a curable or thermoplastic resin includes the steps of: 1, curable or thermoplastic resin And mixing the anatase type titanium dioxide fine particles or a precursor compound of the fine particles with the mixture, and then curing or extruding the mixture (may be heated and melted) in a mold to form the mixture. There is a method in which a homogeneous dispersion or solution is formed, and the solution is placed in a mold and the solvent is removed, or the solution is extruded into a gas or a coagulation bath and molded.
【００１０】Ｅ．人工骨などの製品は、目的との関連で
適宜設計された鋳型を用いて製造しても、ブロック状な
どに成形した材料から、目的との関連で適宜設計された
形状に切り出したり、織・編物、不織布、紙の組織に成
形することにより製造しても良い。このような、成形方
法を選択することにより、硬さ、密度、柔軟性、弾性率
などを調整することもできる。E. Even if products such as artificial bones are manufactured using molds appropriately designed in relation to the purpose, they can be cut out from materials molded in blocks or the like into shapes appropriately designed in relation to the purpose, or can be woven or woven. It may be manufactured by molding into a knitted, nonwoven, or paper structure. By selecting such a molding method, hardness, density, flexibility, elastic modulus, and the like can be adjusted.
【００１１】Ｆ．得られた成形物は、更に生体活性を高
めるために、擬似体液（ＳＢＦ：Ｓimulated Ｂody Ｆl
uid）などのアパタイトに対して過飽和な水溶液中でア
パタイトと同様のＣａ／Ｐ原子比を有するアパタイトを
その表面に形成させて製品とすることができる。F. The obtained molded product was used to further enhance the biological activity by simulating body fluid (SBF: Simulated Body Fl).
apatite having the same Ca / P atomic ratio as apatite in an aqueous solution supersaturated with apatite such as uid) can be obtained as a product.
【００１２】Ｇ、 アパタイトに対して過飽和な水溶液
の一例（擬似体液：ＳＢＦ、ヒトの血漿とほぼ等しい無
機イオン濃度を有する。〔T.Kokubo,H.Kusitani,S.Sakk
a,T.Kitsugi and T.Yamamuro,“Solutions able to rep
roduce in vivo surface-structure changes in bioact
ive glass-ceramic A-W”,J.Biomed,Mater.Res.24,721-
734(1996)〕を表１に示す。G, an example of an aqueous solution supersaturated with respect to apatite (simulated body fluid: SBF, having an inorganic ion concentration approximately equal to that of human plasma. [T. Kokubo, H. Kusitani, S. Sakk]
a, T.Kitsugi and T.Yamamuro, “Solutions able to rep
roduce in vivo surface-structure changes in bioact
ive glass-ceramic AW ”, J.Biomed, Mater.Res.24,721-
734 (1996)] is shown in Table 1.
【００１３】[0013]
【表１】 [Table 1]
【００１４】[0014]
【実施例】実施例１ 前記アナターゼ型二酸化チタン微粒子、Ｔ２００、Ｔ１
００、Ｔ２０およびＴＳとエポキシ系接着剤とを、それ
ぞれ微粒子：樹脂の比が、重量比で３：７となるように
混合し、これを成形枠に入れ、７０℃で２４時間乾燥さ
せてブロックを成形した。これから１０×１０×１ｍｍ
3の試料片を切り出した。該試料片を＃４００研磨紙で
研磨し、アナターゼ型二酸化チタン微粒子を表面に露出
させた試料を得た。これをエタノールなどの液で洗浄し
アナターゼ型酸化チタン微粒子−エポキシ樹脂複合体
〔Ｃ２００（Ｔ２００使用）、Ｃ１００（Ｔ１００使
用）、Ｃ２０（Ｔ２０使用）およびＣＳ（ＴＳ使用）〕
とした。EXAMPLES Example 1 The fine particles of anatase type titanium dioxide, T200, T1
00, T20 and TS and the epoxy-based adhesive were mixed so that the weight ratio of the fine particles to the resin was 3: 7, and the mixture was placed in a molding frame, dried at 70 ° C. for 24 hours, and blocked. Was molded. From now on 10 × 10 × 1mm
Sample No. 3 was cut out. The sample piece was polished with # 400 abrasive paper to obtain a sample in which anatase type titanium dioxide fine particles were exposed on the surface. This is washed with a liquid such as ethanol, and anatase-type titanium oxide fine particles-epoxy resin composite [C200 (using T200), C100 (using T100), C20 (using T20) and CS (using TS)]
And
【００１５】得られた試料を前記擬似体液中に４日間浸
漬した。浸漬前後の試料表面の薄膜Ｘ線回折パターンを
図３（ａ）（ｂ）に示す。浸漬後の試料表面にはアパタ
イトが形成されていることが分かる。The obtained sample was immersed in the simulated body fluid for 4 days. FIGS. 3A and 3B show thin-film X-ray diffraction patterns of the sample surface before and after immersion. It can be seen that apatite is formed on the sample surface after immersion.
【００１６】実施例２ 使用する樹脂を不飽和ポリエステル系樹脂（株式会社マ
ルトー、製品名リゴラック 2004WM-2）とした以外は、
実施例１と同様の操作により、アナターゼ型酸化チタン
微粒子?不飽和ポリエステル系樹脂複合体を作製した
〔Ｐ２００（Ｔ２００使用）、Ｐ１００（Ｔ１００使
用）、Ｐ２０（Ｔ２０使用）およびＰＳ（ＴＳ使
用）〕。得られた試料を、実施例１と同じ条件で擬似体
液に浸漬した。浸漬前後の試料表面の薄膜Ｘ線回折パタ
ーンを図４（ａ）（ｂ）に示す。浸漬後の試料表面には
アパタイトが形成されていることが分かる。Example 2 Except that the resin used was an unsaturated polyester resin (Malteau Co., Ltd., product name Rigolac 2004WM-2)
By the same operation as in Example 1, an anatase-type titanium oxide fine particle-unsaturated polyester resin composite was produced [P200 (using T200), P100 (using T100), P20 (using T20) and PS (using TS)]. . The obtained sample was immersed in a simulated body fluid under the same conditions as in Example 1. FIGS. 4A and 4B show thin-film X-ray diffraction patterns of the sample surface before and after immersion. It can be seen that apatite is formed on the sample surface after immersion.
【００１７】実施例３ 使用する樹脂として変性シリコーン系湿気硬化型１液弾
性接着剤〔セメダイン（株）社製「セメダインスーパー
Ｘ」（商品名）〕系樹脂を用い、酸化チタンとしてＰＳ
を用い実施例１の操作により、アナターゼ型酸化チタン
微粒子−変性シリコーン系湿気硬化型１液接着剤複合体
（ＳＳ）を製造した。得られた試料を、実施例１と同じ
条件で擬似体液に浸漬した。浸漬前後の試料表面の薄膜
Ｘ線回折パターンを図５に示す。浸漬後の試料表面には
アパタイトが形成されていることが分かる。Example 3 A modified silicone moisture-curable one-component elastic adhesive [Cemedine Super X (trade name) manufactured by Cemedine Co., Ltd.] is used as a resin, and PS is used as titanium oxide.
Was used to produce anatase-type titanium oxide fine particles-modified silicone-based moisture-curable one-part adhesive composite (SS). The obtained sample was immersed in a simulated body fluid under the same conditions as in Example 1. FIG. 5 shows thin-film X-ray diffraction patterns of the sample surface before and after immersion. It can be seen that apatite is formed on the sample surface after immersion.
【００１８】[0018]
【発明の効果】以上述べたように、本発明の硬化型樹脂
とアナターゼ型酸化チタン微粒子とを組み合わせ、研磨
により表面に該アナターゼ型酸化チタン微粒子を露出さ
せることにより、擬似体液などのアパタイトに対して過
飽和な水溶液中でアパタイトを形成し得る、安定な人工
骨などとして有用な酸化チタン・有機高分子複合体が得
られるという優れた効果がもたらされる。As described above, the curable resin of the present invention is combined with the anatase-type titanium oxide fine particles, and the anatase-type titanium oxide fine particles are exposed on the surface by polishing, so that the apatite such as a simulated body fluid can be removed. An excellent effect of obtaining a titanium oxide-organic polymer composite useful as a stable artificial bone or the like, which can form apatite in a supersaturated aqueous solution, is obtained.
【図１】 Ｔ２００、Ｔ１００、Ｔ２０、ＴＳの表面の
粉末Ｘ線回折パターンFIG. 1 X-ray powder diffraction pattern of the surface of T200, T100, T20, TS
【図２】 Ｔ２００、Ｔ１００、Ｔ２０、ＴＳの表面の
フーリエ変換赤外拡散反射分光スペクトルFIG. 2 shows a Fourier transform infrared diffuse reflection spectrum of the surface of T200, T100, T20, and TS.
【図３】 擬似体液に４日間浸漬前（ａ）後（ｂ）のア
ナターゼ型酸化チタン微粒子−エポキシ樹脂複合体〔Ｃ
２００（Ｔ２００使用）、Ｃ１００（Ｔ１００使用）、
Ｃ２０（Ｔ２０使用）およびＣＳ（ＴＳ使用）〕表面の
薄膜Ｘ線回折パターンFIG. 3 shows an anatase-type titanium oxide fine particle-epoxy resin composite [C] before (a) and after (b) immersion in a simulated body fluid for 4 days.
200 (using T200), C100 (using T100),
C20 (using T20) and CS (using TS)] Thin film X-ray diffraction pattern on the surface
【図４】 擬似体液に４日間浸漬前（ａ）後（ｂ）のア
ナターゼ型酸化チタン微粒子−ポリエステル系樹脂複合
体〔Ｐ２００（Ｔ２００使用）、Ｐ１００（Ｔ１００使
用）、Ｐ２０（Ｔ２０使用）およびＰＳ（ＴＳ使用）〕
表面の薄膜Ｘ線回折パターンFIG. 4 shows an anatase-type titanium oxide fine particle-polyester resin composite [P200 (using T200), P100 (using T100), P20 (using T20) and PS] before (a) and after (b) immersion in a simulated body fluid for 4 days. (Using TS)]
Thin film X-ray diffraction pattern on the surface
【図５】 擬似体液に４日間浸漬前（ａ）後（ｂ）のア
ナターゼ型酸化チタン微粒子−変性シリコーン系湿気硬
化型１液接着剤複合体表面の薄膜Ｘ線回折パターンFIG. 5 is a thin-film X-ray diffraction pattern on the surface of an anatase-type titanium oxide fine particle-modified silicone-based moisture-curable one-part adhesive composite before (a) and after (b) immersion in a simulated body fluid for four days.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｃ０８Ｊ 7/06 Ｃ０８Ｊ 7/06 Ｚ Ｃ０８Ｋ 3/22 Ｃ０８Ｋ 3/22 Ｃ０８Ｌ 101/00 Ｃ０８Ｌ 101/00 Ｆターム(参考） 4C081 AB04 BB07 CA02 CA03 CA05 CA09 CA16 CA23 CA27 CB01 CB02 CF14 DA01 DA02 DA04 DA06 DB07 4F006 AA11 AA12 AA15 AA32 AA34 AA35 AA36 AA38 AA42 AA55 AB77 BA00 CA09 EA04 4F071 AA02 AA03 AA42 AA49 AA67 AB18 AE17 AH19 BB01 BB06 BC01 BC07 4F073 AA06 AA08 BA06 BA19 BA22 BA23 BA26 BA29 BA33 BA47 BB01 BB02 GA05 4J002 BB001 BC031 BC061 BN151 CB001 CD001 CF001 CF211 CG001 CL001 CP031 DE136 FD016 GB01 ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 7 Identification symbol FI Theme coat ゛ (Reference) C08J 7/06 C08J 7/06 Z C08K 3/22 C08K 3/22 C08L 101/00 C08L 101/00 F term (Ref.) AA06 AA08 BA06 BA19 BA22 BA23 BA26 BA29 BA33 BA47 BB01 BB02 GA05 4J002 BB001 BC031 BC061 BN151 CB001 CD001 CF001 CF211 CG001 CL001 CP031 DE136 FD016 GB01
Claims (8)
粒子または該微粒子の前駆体化合物と硬化性または熱可
塑性樹脂とからなる配合物を用いて成形した、または該
成形物から切り出された物または該成形物を組織化した
複合材料を、機械的研磨または／および化学的処理によ
り複合材料の表面に擬似体液などのアパタイトに対して
過飽和な水溶液中または体内においてアパタイト形成能
を持つアナターゼ型二酸化チタン微粒子を露出させて得
られる酸化チタン・有機高分子複合体。Claims 1. An article molded or cut out from at least an anatase-type titanium dioxide fine particle or a compound comprising a precursor compound of the fine particle and a curable or thermoplastic resin, or a molded article cut out from the molded article. The structured composite material is subjected to mechanical polishing or / and chemical treatment to expose anatase-type titanium dioxide fine particles having an apatite-forming ability in an aqueous solution supersaturated with respect to apatite such as a simulated body fluid or in the body by mechanical polishing or / and chemical treatment. Titanium oxide / organic polymer composite obtained by
樹脂、飽和または不飽和ポリエステル系樹脂、ポリアミ
ド系樹脂、シリコーン樹脂、ポリオレフィン系樹脂、ポ
リスチレン、アクリロニトリル−ブタジエン−スチレン
共重合体樹脂、アクリロニトリル−スチレン共重合体樹
脂、ポリカーボネート系樹脂、ポリアセタールからなる
群から選択される該酸化チタン光触媒特性による酸化・
還元作用により実質的に劣化しない少なくとも１種の樹
脂であることを特徴とする請求項１に記載の酸化チタン
・有機高分子複合体。2. The curable or thermoplastic resin is an epoxy resin, saturated or unsaturated polyester resin, polyamide resin, silicone resin, polyolefin resin, polystyrene, acrylonitrile-butadiene-styrene copolymer resin, acrylonitrile-styrene. Oxidation by photocatalytic properties of the titanium oxide selected from the group consisting of a copolymer resin, a polycarbonate resin, and a polyacetal.
The titanium oxide / organic polymer composite according to claim 1, wherein the composite is at least one resin that does not substantially deteriorate by a reducing action.
ー、テープ、またはフィラメント状の物であり、該成形
物から切り出された物および組織化された物がスライバ
ー、ヤーン、不織布、２次元または３次元織編物である
ことを特徴とする請求項１または２に記載の酸化チタン
・有機高分子複合体。3. The molded article is a block, sheet, fiber, tape, or filamentous article, and an object cut and organized from the molded article is a sliver, a yarn, a nonwoven fabric, two-dimensional or three-dimensional. The titanium oxide / organic polymer composite according to claim 1 or 2, which is a woven or knitted fabric.
ドブラストから選択される少なくとも１種からなること
を特徴とする請求項１、２または３に記載の酸化チタン
・有機高分子複合体。4. The titanium oxide / organic polymer composite according to claim 1, wherein the polishing means comprises at least one selected from a polishing sheet, an abrasive, and sandblast.
粒径１００μｍ〜１０ｎｍのサイズであることを特徴と
する請求項１〜４のいずれかに記載の酸化チタン・有機
高分子複合体。5. The titanium oxide-organic polymer composite according to claim 1, wherein the anatase type titanium dioxide fine particles have a mean particle size of 100 μm to 10 nm.
酸化チタン・有機高分子複合体の人工骨としての使用。6. Use of the titanium oxide / organic polymer composite according to claim 1, 2, 3, 4 or 5 as an artificial bone.
接触によりアパタイト層が表面に形成されたことを特徴
とする請求項１から６のいずれかに記載の酸化チタン・
有機高分子複合体。7. The titanium oxide according to claim 1, wherein an apatite layer is formed on the surface by contact with a supersaturated aqueous solution of apatite.
Organic polymer complex.
似体液であることを特徴とする請求項７記載の酸化チタ
ン・有機高分子複合体。8. The titanium oxide / organic polymer composite according to claim 7, wherein the aqueous solution supersaturated with respect to apatite is a simulated body fluid.
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|---|---|---|---|
| JP2001135160A JP4017836B2 (en) | 2001-05-02 | 2001-05-02 | Titanium oxide organic polymer composite suitable for artificial bones |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001135160A JP4017836B2 (en) | 2001-05-02 | 2001-05-02 | Titanium oxide organic polymer composite suitable for artificial bones |
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| Publication Number | Publication Date |
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| JP4017836B2 JP4017836B2 (en) | 2007-12-05 |
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