JPH0360273B2 - - Google Patents
Info
- Publication number
- JPH0360273B2 JPH0360273B2 JP61311650A JP31165086A JPH0360273B2 JP H0360273 B2 JPH0360273 B2 JP H0360273B2 JP 61311650 A JP61311650 A JP 61311650A JP 31165086 A JP31165086 A JP 31165086A JP H0360273 B2 JPH0360273 B2 JP H0360273B2
- Authority
- JP
- Japan
- Prior art keywords
- ceramic
- alloy
- calcium phosphate
- biometal
- base
- 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.)
- Expired - Lifetime
Links
- 239000000919 ceramic Substances 0.000 claims description 24
- 239000000835 fiber Substances 0.000 claims description 24
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 claims description 17
- 239000001506 calcium phosphate Substances 0.000 claims description 16
- 239000007943 implant Substances 0.000 claims description 14
- 229910000389 calcium phosphate Inorganic materials 0.000 claims description 13
- 235000011010 calcium phosphates Nutrition 0.000 claims description 13
- 229910001069 Ti alloy Inorganic materials 0.000 claims description 8
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 claims description 6
- 229910052586 apatite Inorganic materials 0.000 claims description 5
- 239000010935 stainless steel Substances 0.000 claims description 5
- 239000002131 composite material Substances 0.000 claims description 4
- 229910001220 stainless steel Inorganic materials 0.000 claims description 4
- 229910045601 alloy Inorganic materials 0.000 claims 1
- 239000000956 alloy Substances 0.000 claims 1
- 239000002585 base Substances 0.000 description 13
- 210000000988 bone and bone Anatomy 0.000 description 6
- 239000011575 calcium Substances 0.000 description 5
- 229910000599 Cr alloy Inorganic materials 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 229910000391 tricalcium phosphate Inorganic materials 0.000 description 3
- 235000019731 tricalcium phosphate Nutrition 0.000 description 3
- 229940078499 tricalcium phosphate Drugs 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 241000283973 Oryctolagus cuniculus Species 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000002316 cosmetic surgery Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- -1 etc. are dispersed Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 229910052587 fluorapatite Inorganic materials 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000001513 hot isostatic pressing Methods 0.000 description 1
- 210000004969 inflammatory cell Anatomy 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 210000002540 macrophage Anatomy 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- 230000000399 orthopedic effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910001256 stainless steel alloy Inorganic materials 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000001356 surgical procedure Methods 0.000 description 1
- 210000001519 tissue Anatomy 0.000 description 1
- 210000000689 upper leg Anatomy 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Landscapes
- Laminated Bodies (AREA)
- Manufacture Of Alloys Or Alloy Compounds (AREA)
- Materials For Medical Uses (AREA)
- Dental Prosthetics (AREA)
Description
【発明の詳細な説明】
「産業上の利用分野」
歯科、成形外科における医療用インプラントの
改良に関する。DETAILED DESCRIPTION OF THE INVENTION "Field of Industrial Application" This invention relates to improvements in medical implants in dentistry and plastic surgery.
「従来の技術」
従来、Co−Cr合金、Ti合金、ステンレス製の
インプラントが多数医療分野で使用されている
が、長期間体内に埋設されると体内の組織液や体
液によつて、あるいは体内の組織体との摩擦によ
つてインプラントが腐食し、インプラントの成分
イオンが体内に溶出し、マクロフアージが損傷し
たり、細胞内に侵入して炎症性細胞や巨大細胞の
発生原因となるものである。そこで、インプラン
ト材の表面にコーテイング等の表面処理を施し、
インプラント材の成分イオンの溶出を防止する方
法が種々提案されている。（特公昭49−24429、特
開昭59−82849、特開昭61−76354）
「発明が解決しようとする問題点」
しかしながら、前期発明によつても、未だ耐蝕
性、耐久性、生体親和性が不十分であり、特に長
期間の使用が行なわれる整形外科用としては不完
全であつた。``Conventional technology'' Conventionally, many implants made of Co-Cr alloy, Ti alloy, and stainless steel have been used in the medical field. Implants corrode due to friction with tissues, and component ions of the implants are eluted into the body, damaging macrophages and penetrating into cells, causing the generation of inflammatory cells and giant cells. Therefore, surface treatments such as coating are applied to the surface of the implant material.
Various methods have been proposed for preventing the elution of component ions of implant materials. (Japanese Patent Publications No. 49-24429, No. 59-82849, No. 61-76354) "Problems to be solved by the invention" However, even with earlier inventions, corrosion resistance, durability, and biocompatibility still remain. It was insufficient for orthopedic surgery, especially for long-term use.
この発明は上記従来のものの欠点を改良するも
のであり、インプラントの耐蝕性、耐久性、生体
親和性を向上させ、インプラントの長期間にわた
る安全使用を可能とするものである。 The present invention improves the above-mentioned drawbacks of the conventional implants, improves the corrosion resistance, durability, and biocompatibility of the implant, and enables safe use of the implant over a long period of time.
「問題点を解決するための手段」
セラミツクフアイバー等を分散したCo−Cr合
金、ステンレス、Ti合金等の生体金属よりなる
基体と、その外面に、基体中のセラミツクフアイ
バー等と同質で、一端を基体中に埋入し他方をア
パタイト又は燐酸カルシウム中に突出する第２相
と、その外面をおおう、アパタイト又は燐酸カル
シウム層とよりなるセラミツク複合インプラント
であり、特に好ましいものは、セラミツクフアイ
バー等が、SiC又はSi3N4のウイスカー又はフア
イバーであるが、本発明はこれに拘らず、
Al2O3、ZrO2ムライト等のフアイバーやウイスカ
ー（以下単に「セラミツクフアイバー」と略称す
る）でも良好なものである。``Means for solving the problem'' A base made of a biometal such as a Co-Cr alloy, stainless steel, or a Ti alloy in which ceramic fibers, etc. are dispersed, and a base made of a biometal such as a Co-Cr alloy, stainless steel, or a Ti alloy, with ceramic fibers, etc. in the base body, and one end A ceramic composite implant consisting of a second phase embedded in a base body and protruding from apatite or calcium phosphate on the other side, and an apatite or calcium phosphate layer covering the outer surface of the second phase, and particularly preferred is a ceramic fiber or the like. SiC or Si 3 N 4 whiskers or fibers, but the present invention is not limited thereto.
Fibers and whiskers (hereinafter simply referred to as "ceramic fibers") such as Al 2 O 3 and ZrO 2 mullite are also suitable.
「作用」
セラミツクフアイバーは一端を基体のマトリツ
クスを構生するCo−Cr合金、ステンレス、Ti合
金（以下まとめて「生体金属」と称する。）中に
埋入し、他端を、アパタイト又は燐酸カルシウム
（以下まとめて「HAP」と略称する）の中に有す
るため、生体金属とHAPとはセラミツクフアイ
バーを介して強固に結合され、長年月の応力に対
してもはがれることがない。"Function" One end of the ceramic fiber is embedded in a Co-Cr alloy, stainless steel, or Ti alloy (hereinafter collectively referred to as "biometal") that makes up the base matrix, and the other end is embedded in apatite or calcium phosphate. (hereinafter collectively referred to as "HAP"), the biometal and HAP are firmly bonded via ceramic fibers, and will not separate even under stress over many years.
「実施例」
一例として生体金属にTi合金、セラミツクフ
アイバーに長さ100μのSiCウイスカー、HAPに
トリカルシウムフオスフエート3CaO・P2O5を用
いたものを説明する。"Example" As an example, a case will be described in which a Ti alloy is used as the biometal, a SiC whisker with a length of 100 μ is used as the ceramic fiber, and tricalcium phosphate 3CaO.P 2 O 5 is used as the HAP.
Ti合金の平均粒径100μの粉末50体積％とSiCウ
イスカー50体積％とをアセトン中でよく混合し、
乾燥後３mmφ×25mmの棒状に、静水圧加圧成形
し、次に真空中で白金箔中に封入する。これを
1400℃にて1000気圧で熱間静水圧成形（以下
「HIP」と略称する）し2.5mmφ×23mmの棒状焼
結体とした。これを研摩して断面を観察すれば第
２図のように生体金属２によるマトリツクスの中
に、セラミツクフアイバー３が分散した基体１を
形成していた。 50% by volume of Ti alloy powder with an average particle size of 100μ and 50% by volume of SiC whiskers are thoroughly mixed in acetone,
After drying, it is hydrostatically pressed into a rod shape of 3 mmφ x 25 mm, and then sealed in platinum foil in a vacuum. this
Hot isostatic pressing (hereinafter referred to as "HIP") was performed at 1400°C and 1000 atm to form a rod-shaped sintered body of 2.5 mmφ x 23 mm. When this was polished and the cross section was observed, it was found that a base 1 was formed in which ceramic fibers 3 were dispersed in a matrix of biometal 2 as shown in FIG.
次にこの表面を約20μの深さ迄、弗化水素酸に
てエツチングしたところ、第３図の如く、セラミ
ツクフアイバーの一端４は生体金属中に埋入し、
他端５が空中に突出した表面を形成した。 Next, this surface was etched to a depth of approximately 20μ with hydrofluoric acid, and as shown in Fig. 3, one end 4 of the ceramic fiber was embedded in the biometal.
The other end 5 formed a surface protruding into the air.
次にCaCO3とP2O5を、Ca／Ｐ原子比が1.5とな
るように調合し粉砕して混合し、50％の水と有機
結合剤を加えて泥しようとし、前記基体を浸漬す
ることにより約0.3mmの厚さに付着させ、乾燥後
1100℃にて大気中で焼きつけた。この断面を顕微
鏡で観察すれば第１図のように基体１の上に一端
を主体金属に埋入し、他端をHAP中に突出した
セラミツクフアイバー３とその外側に被覆したト
リカルシウムフオスフエート層６を有するセラミ
ツク複合インプラント７を構成していた。これを
成兎の大腿骨中に埋入したところ、約１カ月でト
リカルシウムフオスフエートは骨に転化し始めて
いた。又同じ方法で20mm×20mm×５mmの直方体の
テストピースを作成しその主表面にゴム板を接着
し、10Kgの力で引張ることを40回繰り返したが剥
離することはなかつた。併し比較のため、弗化水
素酸による生体金属の表面を溶解することを省い
たものは10回の引張りで剥離を起こした。これ
は、本発明の、一端４を生体金属中に埋入し、他
端５を突出するセラミツクフアイバーがないため
に、生体金属とHAPとを強靭に接着するものが
なかつたためである。 Next, prepare CaCO 3 and P 2 O 5 so that the Ca/P atomic ratio is 1.5, grind and mix, add 50% water and an organic binder to make a slurry, and immerse the substrate. After drying, adhere to a thickness of about 0.3 mm.
Baked in air at 1100℃. If this cross section is observed under a microscope, as shown in Figure 1, there is a ceramic fiber 3 on the base 1 with one end embedded in the main metal and the other end protruding into the HAP, and the tricalcium phosphate coated on the outside. A ceramic composite implant 7 having a layer 6 was constructed. When this was implanted into the femur of an adult rabbit, the tricalcium phosphate began to convert into bone in about one month. In addition, a rectangular parallelepiped test piece measuring 20 mm x 20 mm x 5 mm was prepared using the same method, a rubber plate was glued to the main surface of the test piece, and the test piece was pulled with a force of 10 kg 40 times, but no peeling occurred. However, for comparison, a sample in which the biometal surface was not dissolved with hydrofluoric acid caused peeling after 10 pulls. This is because there is no ceramic fiber in the present invention in which one end 4 is embedded in the biometal and the other end 5 protrudes, so there is nothing to strongly bond the biometal and the HAP.
また燐酸カルシウム塩については本実施例の他
に、特開昭55−56052号「高強度リン酸カルシウ
ム焼結体の製造方法」において開示したCa／Ｐ
原子比が1.4乃至1.75のカルシウムのリン酸塩を
主体とする粉末に、焼成後のリン酸カルシウム成
分に対し0.5乃至15重量％のCa／Ｐ原子比0.2乃至
0.75を有するカルシウム、リン酸系フリツトを添
加混合し、溶融する特に強度の強いもの、又は上
記リン酸カルシウムに0.5乃至15重５重量％のア
ルカリ金属、亜鉛又はアルカリ土類金属の酸化物
−リン酸系フリツトを含有せしめたもの（特開昭
55−140756号「高強度リン酸カルシウム焼結体」）
又は、特開昭55−80771号「高強度リン酸カルシ
ウム焼結体」において開示したカルシウムのリン
酸塩を主体とする粉末と上記リン酸カルシウムガ
ラスやアルカリ土類金属酸化物−リン酸系フリツ
トの混合物でもよい。更にアパタイトグループ
（水酸アパタイト、弗素アパタイト等）特に、水
酸アパタイトCa10（OO4）6（OH）2も好ましいもの
である。 Regarding calcium phosphate salt, in addition to this example, Ca/P disclosed in JP-A No. 55-56052 ``Method for manufacturing high-strength calcium phosphate sintered body''
A powder mainly composed of calcium phosphate with an atomic ratio of 1.4 to 1.75 is added with a Ca/P atomic ratio of 0.2 to 0.5 to 15% by weight based on the calcium phosphate component after firing.
0.75, a particularly strong one by adding and mixing calcium or phosphate-based frit and melting, or 0.5 to 15% by weight of alkali metal, zinc or alkaline earth metal oxide-phosphoric acid to the above calcium phosphate Contains frits (JP-A-Sho)
No. 55-140756 “High-strength calcium phosphate sintered body”)
Alternatively, it may be a mixture of the powder mainly composed of calcium phosphate disclosed in JP-A No. 55-80771 "High Strength Calcium Phosphate Sintered Body" and the above-mentioned calcium phosphate glass or alkaline earth metal oxide-phosphoric acid frit. . Furthermore, apatite groups (hydroxyapatite, fluoroapatite, etc.), especially hydroxyapatite Ca 10 (OO 4 ) 6 (OH) 2 are also preferred.
なお、セラミツクフアイバーは20〜70体積％が
好ましく、20％以下ではその効果が少なく、70％
を超えると基体の成形性を害する。 In addition, the ceramic fiber is preferably 20 to 70% by volume, and if it is less than 20%, the effect will be small;
Exceeding this will impair the moldability of the substrate.
「効果」
以上のとおりの構成を有するので、下記の大き
な効果を有する。"Effects" With the configuration as described above, it has the following great effects.
(1) 基体はTi合金の他に、セラミツクフアイバ
ーを含むので、強度は向上し、且つ比重は低く
なるために骨の比重である3.1に近くなり生体
に違和感を生じることが少ない。(1) Since the base body includes ceramic fibers in addition to Ti alloy, the strength is improved and the specific gravity is low, so it is close to the specific gravity of bone, which is 3.1, and there is less discomfort in the body.
(2) 基体とHAPとを強固に接合し、長年月の応
力に対しても剥離を起さない。(2) The base and HAP are firmly bonded and will not peel off even under stress over many years.
(3) 表面のHAPにより生体親和性が高く、骨に
転化して骨とよく結合する。(3) It has high biocompatibility due to HAP on the surface, converts into bone, and integrates well with bone.
(4) 表面のHAPが骨に転化した後もセラミツク
フアイバーがHAPと生体金属との間に存在し
骨と生体金属が直接接触することを防ぐ。(4) Even after HAP on the surface is converted into bone, ceramic fibers exist between HAP and biometal to prevent direct contact between bone and biometal.
第１図は本発明のインプラントの断面の微少構
造を示す略図。第２図は基体を成形した状態の断
面図、第３図は成形後、表面を溶解除去したもの
の断面図。
１……基体、２……生体金属、３……セラミツ
クフアイバー、４……セラミツクフアイバーの基
体に埋入した一端、５……セラミツクフアイバー
の基体より突出した一体、６……HAP層、７…
…本発明品。
FIG. 1 is a schematic diagram showing the cross-sectional microstructure of the implant of the present invention. FIG. 2 is a cross-sectional view of the base after it has been molded, and FIG. 3 is a cross-sectional view of the base after the surface has been dissolved and removed after molding. DESCRIPTION OF SYMBOLS 1... Base body, 2... Biometal, 3... Ceramic fiber, 4... One end embedded in the base body of the ceramic fiber, 5... An integral part protruding from the base body of the ceramic fiber, 6... HAP layer, 7...
...Product of the present invention.
Claims (1)
合金、ステンレス、Ti合金等の生体金属よりな
る基体と、その外面に、基体中のセラミツクフア
イバー等と同質で、一端を基体中に埋入し、他方
をアパタイト又は燐酸カルシウム中に突出する第
２相と、その外面をおおう、アパタイト又は燐酸
カルシウム層とよりなるセラミツク複合インプラ
ント。 ２ セラミツクフアイバー等は、SiC又はSi3N4
よりなるフアイバー又はウイスカーである特許請
求の範囲第１項記載のセラミツク複合インプラン
ト。[Claims] 1. Co-Cr with ceramic fibers etc. dispersed therein.
A base made of a biometal such as an alloy, stainless steel, or a Ti alloy, and a second fiber on its outer surface that is the same as the ceramic fiber in the base and has one end embedded in the base and the other protruding into apatite or calcium phosphate. Ceramic composite implant consisting of a phase and an apatite or calcium phosphate layer covering its outer surface. 2 Ceramic fiber etc. are SiC or Si 3 N 4
The ceramic composite implant according to claim 1, which is a fiber or whisker consisting of.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61311650A JPS63161971A (en) | 1986-12-26 | 1986-12-26 | Ceramic composite implant |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61311650A JPS63161971A (en) | 1986-12-26 | 1986-12-26 | Ceramic composite implant |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63161971A JPS63161971A (en) | 1988-07-05 |
| JPH0360273B2 true JPH0360273B2 (en) | 1991-09-13 |
Family
ID=18019834
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61311650A Granted JPS63161971A (en) | 1986-12-26 | 1986-12-26 | Ceramic composite implant |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63161971A (en) |
-
1986
- 1986-12-26 JP JP61311650A patent/JPS63161971A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63161971A (en) | 1988-07-05 |
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| Date | Code | Title | Description |
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| LAPS | Cancellation because of no payment of annual fees |