JPH04126157A - Inorganic biomaterial - Google Patents
Inorganic biomaterialInfo
- Publication number
- JPH04126157A JPH04126157A JP2248348A JP24834890A JPH04126157A JP H04126157 A JPH04126157 A JP H04126157A JP 2248348 A JP2248348 A JP 2248348A JP 24834890 A JP24834890 A JP 24834890A JP H04126157 A JPH04126157 A JP H04126157A
- Authority
- JP
- Japan
- Prior art keywords
- glass
- crystallized glass
- zirconia
- strength
- cao
- 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.)
- Pending
Links
- 239000012620 biological material Substances 0.000 title claims abstract description 13
- 239000011521 glass Substances 0.000 claims abstract description 107
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 72
- 239000000919 ceramic Substances 0.000 claims abstract description 63
- 239000002131 composite material Substances 0.000 claims abstract description 45
- 239000011247 coating layer Substances 0.000 claims abstract description 21
- 239000000203 mixture Substances 0.000 claims description 17
- 210000000988 bone and bone Anatomy 0.000 claims description 11
- 230000000975 bioactive effect Effects 0.000 abstract description 19
- 238000000576 coating method Methods 0.000 abstract description 18
- 239000011248 coating agent Substances 0.000 abstract description 17
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 abstract description 16
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 10
- 229910052593 corundum Inorganic materials 0.000 abstract description 8
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract description 8
- 229910052681 coesite Inorganic materials 0.000 abstract description 5
- 229910052906 cristobalite Inorganic materials 0.000 abstract description 5
- 239000000377 silicon dioxide Substances 0.000 abstract description 5
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 5
- 229910052682 stishovite Inorganic materials 0.000 abstract description 5
- 229910052905 tridymite Inorganic materials 0.000 abstract description 5
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 abstract 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 abstract 2
- 239000000843 powder Substances 0.000 description 26
- 239000013078 crystal Substances 0.000 description 25
- 239000010410 layer Substances 0.000 description 19
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 16
- 239000002245 particle Substances 0.000 description 15
- 239000011162 core material Substances 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- 239000002002 slurry Substances 0.000 description 10
- 229910052586 apatite Inorganic materials 0.000 description 9
- 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 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 229910019142 PO4 Inorganic materials 0.000 description 8
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 8
- 150000002222 fluorine compounds Chemical class 0.000 description 8
- 239000000156 glass melt Substances 0.000 description 8
- 150000004677 hydrates Chemical class 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 235000021317 phosphate Nutrition 0.000 description 8
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 8
- 229910052697 platinum Inorganic materials 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000005452 bending Methods 0.000 description 7
- 230000007423 decrease Effects 0.000 description 7
- 238000002513 implantation Methods 0.000 description 7
- 238000005245 sintering Methods 0.000 description 7
- 241000282472 Canis lupus familiaris Species 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229910002077 partially stabilized zirconia Inorganic materials 0.000 description 5
- 230000000844 anti-bacterial effect Effects 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 210000000214 mouth Anatomy 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 239000010456 wollastonite Substances 0.000 description 4
- 229910052882 wollastonite Inorganic materials 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 239000006061 abrasive grain Substances 0.000 description 3
- 229910003460 diamond Inorganic materials 0.000 description 3
- 239000010432 diamond Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000007943 implant Substances 0.000 description 3
- 238000013001 point bending Methods 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- RBNCTJWRWOMIBO-UHFFFAOYSA-N dicalcium;magnesium;trihydroxy(trihydroxysilyloxy)silane Chemical compound [Mg+2].[Ca+2].[Ca+2].O[Si](O)(O)O[Si](O)(O)O RBNCTJWRWOMIBO-UHFFFAOYSA-N 0.000 description 2
- 238000004455 differential thermal analysis Methods 0.000 description 2
- 229910052839 forsterite Inorganic materials 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 2
- 230000011164 ossification Effects 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 description 2
- 210000001519 tissue Anatomy 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 210000000689 upper leg Anatomy 0.000 description 2
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910052661 anorthite Inorganic materials 0.000 description 1
- 239000005313 bioactive glass Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- NWXHSRDXUJENGJ-UHFFFAOYSA-N calcium;magnesium;dioxido(oxo)silane Chemical compound [Mg+2].[Ca+2].[O-][Si]([O-])=O.[O-][Si]([O-])=O NWXHSRDXUJENGJ-UHFFFAOYSA-N 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- GWWPLLOVYSCJIO-UHFFFAOYSA-N dialuminum;calcium;disilicate Chemical compound [Al+3].[Al+3].[Ca+2].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] GWWPLLOVYSCJIO-UHFFFAOYSA-N 0.000 description 1
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 description 1
- 229910052637 diopside Inorganic materials 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002241 glass-ceramic Substances 0.000 description 1
- 238000001513 hot isostatic pressing Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 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 description 1
- 239000001993 wax Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C4/00—Compositions for glass with special properties
- C03C4/0007—Compositions for glass with special properties for biologically-compatible glass
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61C—DENTISTRY; APPARATUS OR METHODS FOR ORAL OR DENTAL HYGIENE
- A61C8/00—Means to be fixed to the jaw-bone for consolidating natural teeth or for fixing dental prostheses thereon; Dental implants; Implanting tools
- A61C8/0012—Means to be fixed to the jaw-bone for consolidating natural teeth or for fixing dental prostheses thereon; Dental implants; Implanting tools characterised by the material or composition, e.g. ceramics, surface layer, metal alloy
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61C—DENTISTRY; APPARATUS OR METHODS FOR ORAL OR DENTAL HYGIENE
- A61C8/00—Means to be fixed to the jaw-bone for consolidating natural teeth or for fixing dental prostheses thereon; Dental implants; Implanting tools
- A61C8/0012—Means to be fixed to the jaw-bone for consolidating natural teeth or for fixing dental prostheses thereon; Dental implants; Implanting tools characterised by the material or composition, e.g. ceramics, surface layer, metal alloy
- A61C8/0013—Means to be fixed to the jaw-bone for consolidating natural teeth or for fixing dental prostheses thereon; Dental implants; Implanting tools characterised by the material or composition, e.g. ceramics, surface layer, metal alloy with a surface layer, coating
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C14/00—Glass compositions containing a non-glass component, e.g. compositions containing fibres, filaments, whiskers, platelets, or the like, dispersed in a glass matrix
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/02—Surface treatment of glass, not in the form of fibres or filaments, by coating with glass
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/062—Glass compositions containing silica with less than 40% silica by weight
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/062—Glass compositions containing silica with less than 40% silica by weight
- C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/097—Glass compositions containing silica with 40% to 90% silica, by weight containing phosphorus, niobium or tantalum
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/11—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen
- C03C3/112—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing fluorine
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/11—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen
- C03C3/112—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing fluorine
- C03C3/115—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing fluorine containing boron
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野コ
本発明は、人工歯根および人工骨などのインブラント材
料として有用な、高強度で生体活性機能の高い無機生体
材料に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to an inorganic biomaterial with high strength and high bioactivity that is useful as an implant material such as an artificial tooth root and an artificial bone.
［従来の技術］
従来、強度を高めた生体活性な結晶化ガラスとして、生
体活性な結晶化ガラスとジルコニア系セラミックスを複
合焼結させた材料が開発されている（特開昭６２−２３
１６６８号、特開平１−９１８６５号、特開平１−１１
５３６０号の各公報参照）。この複合材料はジルコニア
含有量によって、２３０〜Ｌ４００ＭＰａと高い曲げ強
度を有している。[Prior art] Conventionally, a composite sintered material of bioactive crystallized glass and zirconia ceramics has been developed as bioactive crystallized glass with increased strength (Japanese Unexamined Patent Publication No. 62-23
No. 1668, JP-A-1-91865, JP-A-1-11
(Refer to each publication of No. 5360). This composite material has a high bending strength of 230 to 400 MPa depending on the zirconia content.
一方、生体用結晶化ガラスの強度を向上させる他の方法
として、特開昭６１−２２６０５３号公報には、芯体を
ジルコニアセラミックスとし、その表面にＣａＯ−Ｐ２
Ｏ５系結晶化ガラスをコーティングする方法も示されて
いる。On the other hand, as another method for improving the strength of crystallized glass for biological use, Japanese Patent Application Laid-Open No. 61-226053 discloses that the core is made of zirconia ceramics and the surface is coated with CaO-P2.
A method of coating O5-based crystallized glass is also shown.
［発明が解決しようとする課題］
上記特開昭６２−２３１６８８号、特開平１−９１８１
３５号、特開平１−１１５３８０号の各公報記載の、ジ
ルコニア系セラミックスを分散させることによって結晶
化ガラスの強度を向上させた高強度複合セラミックスで
は、生体活性に寄与する結晶化ガラスの量は減少するこ
とになるので、ある程度生体活性を犠牲に巳なければな
らず、長期に亘る生体活性機能は十分であるるものの、
埋入後の早い時間（約１ケ月）の生体活性が劣り、骨と
結合するまでに時間がかかるため、治療が遅れることに
なる。例えば、人工歯根として使用した場合、早い時期
では骨と結合していないため人工歯根の上部に歯冠を設
けることができない。[Problem to be solved by the invention] The above-mentioned JP-A-62-231688, JP-A-1-9181
In the high-strength composite ceramics in which the strength of crystallized glass is improved by dispersing zirconia-based ceramics, as described in the publications No. 35 and JP-A-1-115380, the amount of crystallized glass that contributes to bioactivity is reduced. Therefore, bioactivity must be sacrificed to some extent, and although the long-term bioactivity function is sufficient,
Bioactivity is poor in the early period after implantation (approximately one month), and it takes time for it to integrate with the bone, resulting in a delay in treatment. For example, when used as an artificial tooth root, it is not possible to provide a crown on the top of the artificial tooth root because it is not integrated with the bone at an early stage.
一方、特開昭６１−２２６０５３号公報記載の方法では
、本来ジルコニアセラミックスは１０００〜２Ｏ００Ｍ
Ｐａという高強度であるにもかかわらず、生体活性な結
晶化ガラス層が厚すぎて、ジルコニアセラミックスの高
強度性を十分に生かすことができず、５００〜７００Ｍ
Ｐａ程度の強度に留ってしまう。これは、材料強度が厚
い結晶化ガラス層に存在する疵に大きく影響されてしま
うためである。大きな力がかかったとき、厚い脆弱な結
晶化ガラス層を亀裂が進行する速度は大きくかつ加速さ
れ、すぐにジルコニアセラミック芯体に衝突するが、そ
の亀裂の進行速度が大きいために、その進展を止められ
ず、ジルコニアセラミックス部分をも破壊するからであ
る。そこで、被覆方法を工夫して結晶化ガラス層を薄く
できた場合には、大きな疵が入りにくく、また結晶化ガ
ラス層内での亀裂の加速は少ないため、強度は向上でき
るが、生体活性は約３ケ月以内の初期だけしか発揮され
ず、長期になると、結晶化ガラス層がすべて生体組織に
吸収され、生体活性機能を失ってしまうという欠点があ
る。On the other hand, in the method described in JP-A No. 61-226053, zirconia ceramics are originally
Despite the high strength of 500 to 700 M, the bioactive crystallized glass layer is too thick to take full advantage of the high strength of zirconia ceramics.
The strength remains at about Pa. This is because the material strength is greatly affected by flaws existing in the thick crystallized glass layer. When a large force is applied, the speed at which cracks propagate through the thick, brittle crystallized glass layer increases and accelerates, and they immediately collide with the zirconia ceramic core. This is because it cannot be stopped and destroys the zirconia ceramic part. Therefore, if the coating method can be devised to make the crystallized glass layer thinner, large scratches will be less likely to occur, and cracks will not accelerate within the crystallized glass layer, so the strength can be improved, but the bioactivity will be reduced. The drawback is that it is only effective in the initial period of about 3 months, and over a long period of time, the entire crystallized glass layer is absorbed into living tissue and loses its bioactive function.
したがって、高強度でかつ早期から長期に亘って生体活
性機能を発揮し続ける無機生体材料が要望されていた。Therefore, there has been a demand for inorganic biomaterials that have high strength and continue to exhibit bioactive functions from an early stage to a long period of time.
［課題を解決するための手段］
本発明者らは、上記課題を克服するべく検討を重ねた結
果、生体用結晶化ガラスにジルコニア系セラミックスを
分散させた高強度複合セラミックス表面に、生体活性の
高い結晶化ガラスをコーティングすることにより、高強
度でかつ早期から長期に亘って生体活性機能を発揮し続
ける無機生体材料が得られることを見い出した。[Means for Solving the Problems] As a result of repeated studies to overcome the above-mentioned problems, the present inventors have developed a bioactive material on the surface of a high-strength composite ceramic in which zirconia-based ceramics are dispersed in biomedical crystallized glass. We have discovered that by coating with highly crystallized glass, it is possible to obtain an inorganic biomaterial that has high strength and continues to exhibit bioactive functions from an early stage to a long period of time.
本発明の無機生体材料は、重量百分率で、ＣａＯ３１２
〜５６％
Ｐｏ １〜２７％
ＳｉＯ２２２〜５０％
ＭｇＯ０〜３４％
Ａｌ２Ｏ３０〜２５％
の範囲で上記成分を含有し、ＣａＯ，Ｐ２Ｏ５、ＳｉＯ
２、ＭｇＯ及びＡｌ２Ｏ３の含有量合計が９０％以上で
ある組成を有する結晶化ガラス中にジルコニア系セラミ
ックスを分散させた複合セラミックスの表面に、重量百
分率で、
ＣａＯ３１２〜５６％
Ｐ２Ｏ５１〜２７％
Ｓｉ０２２２〜５０％
Ｍ ｇ Ｏ０〜３４％
Ａｌ２Ｏ３０〜２５％
の範囲で上記成分を含有し、Ｃａ２Ｏ５１Ｐ２Ｏ５、Ｓ
ｉＯＭｇＯ及びＡｌ２Ｏ３の含有量合計がＳ
９０％以上である組成を有するガラス又は結晶化ガラス
のコーティング層を設けたことを特徴とする特
本発明の無機生体材料の芯体は、生体用結晶化ガラスに
ジルコニア系セラミックスを分散させた高強度複合セラ
ミックスであって、生体用結晶化ガラスは、重量百分率
で、
Ｃａ Ｏ５１２〜５６％
Ｐ２Ｏ５１〜２７％
５１０２ ２２〜５０％
ＭｇＯ０〜３４％
Ａｌ２Ｏ３０〜２５％
の範囲で上記成分を含有し、Ｃａ２Ｏ５１Ｐ２Ｏ５、Ｓ
ｉＯＭｇＯ及びＡｌ２Ｏ３の含有量合計が９０％以上で
ある組成を有する結晶化ガラスである。これらは、アパ
タイト結晶と、ウオラストナイト、ジオプサイド、フォ
ルステライト、オケルマナイト、アノルサイト等のアル
カリ土類ケイ酸塩結晶の１種または２種以上とを含有し
、さらに場合ニよりβ−リン酸三カルシウム結晶を含有
する。この結晶化ガラスの組成の限定理由は以下の通り
である。ＣａＯが１２％未満では、アパタイト結晶の析
出量が極端に少なくなる。またＣａＯが５６％を越える
とガラスの失透傾向が著しくなる。従って、ＣａＯの含
量は１２〜５６％に限定される。Ｐ２Ｏ５が１％未満で
は、ガラスの失透傾向が著しく、２７％を越えるとウオ
ラストナイト、ジオフサイド、フォルステライト、オケ
ルマナイト、アノルサイト等のアルカリ土類ケイ酸塩結
晶の析出量が少なくなるので、Ｐ２Ｏ５の含量は１〜２
７％に限定される。５１０２が２２％未満では、アルカ
リ土類ケイ酸塩結晶の析出量が少なくなる。またＳ ｉ
Ｏ２が５０％を越えるとガラスが失透しやすくなる。The inorganic biomaterial of the present invention has a weight percentage of CaO312
-56% Po 1-27% SiO22-50% MgO0-34% Al2O30-25% Contains the above components, including CaO, P2O5, SiO
2. On the surface of a composite ceramic in which zirconia ceramics are dispersed in crystallized glass having a composition in which the total content of MgO and Al2O3 is 90% or more, in weight percentage, CaO312~56% P2O51~27% Si0222~ Contains the above components in the range of 50% Mg O0 to 34% Al2O30 to 25%, Ca2O51P2O5, S
The core of the inorganic biomaterial of the present invention is characterized in that it is provided with a coating layer of glass or crystallized glass having a composition in which the total content of iOMgO and Al2O3 is S 90% or more. A high-strength composite ceramic in which zirconia ceramics are dispersed, the biomedical crystallized glass has the following weight percentages: CaO512-56% P2O51-27% 5102 22-50% MgO0-34% Al2O30-25% Contains the above components within the range, Ca2O51P2O5, S
This is a crystallized glass having a composition in which the total content of iOMgO and Al2O3 is 90% or more. These contain apatite crystals and one or more alkaline earth silicate crystals such as wollastonite, diopside, forsterite, okermanite, anorthite, and in some cases β-tricalcium phosphate. Contains crystals. The reasons for limiting the composition of this crystallized glass are as follows. When CaO is less than 12%, the amount of apatite crystals precipitated becomes extremely small. Moreover, when CaO exceeds 56%, the tendency of the glass to devitrify becomes significant. Therefore, the content of CaO is limited to 12-56%. When P2O5 is less than 1%, the glass tends to devitrify significantly, and when it exceeds 27%, the amount of alkaline earth silicate crystals such as wollastonite, geofside, forsterite, okermanite, and anorsite decreases. The content of P2O5 is 1-2
Limited to 7%. When 5102 is less than 22%, the amount of alkaline earth silicate crystals precipitated becomes small. Also, Si
When O2 exceeds 50%, the glass tends to devitrify.
従って、ＳｉＯ２の含量は ２２〜５０％に限定される
。ＭｇＯは必須成分ではないが、含む場合は３４％より
多いとアパタイト結晶の生成量が少なくなるので、３４
％以下に限定される。同様に、Ａｌ２Ｏ３も必須成分で
はないが、含む場合は２５％より多いとアパタイト結晶
の生成量が少なくなるので、２５％以下に限定される。Therefore, the content of SiO2 is limited to 22-50%. MgO is not an essential component, but if it is included, the amount of apatite crystals produced will decrease if it is included.
% or less. Similarly, Al2O3 is not an essential component, but if it is included, the amount of apatite crystals produced will decrease if it is more than 25%, so it is limited to 25% or less.
上記した５成分に加えてガラスは、Ｆ２−０、Ｌｉ２Ｏ
、Ｎａ２Ｏ、Ｔ ｔ ０２、ＺｒＯ２、ＳｒＯ、Ｎｂ２
Ｏ５、Ｔａ２Ｏ５、Ｂ２Ｏ３、Ｆ２、Ｙ２Ｏ３を１０％
の範囲内で一種または二種以上含有することができる。In addition to the five components listed above, glass also contains F2-0, Li2O
, Na2O, T t 02, ZrO2, SrO, Nb2
10% O5, Ta2O5, B2O3, F2, Y2O3
One or more types can be contained within the range of .
これらの任意成分の合計が１０％より多いときには、ア
パタイト結晶及びアルカリ土類ケイ酸塩結晶の生成量か
低下してしまう場合があるので、好ましくは１０％以下
とするのがよい。ただし、Ｆ２は５％より多いとガラス
が失透しやすくなり、またＹ２Ｏ３が５％より多いとア
パタイト結晶及びアルカリ土類ケイ酸塩結晶の生成量が
低下してしまうので、Ｆ２及びＹ２Ｏ３はそれぞれ５％
以下に限定される。そして、上記の結晶化ガラス中に、
ジルコニア系高強度セラミックスを分散させた複合セラ
ミックスは、アルミナセラミックス、ジルコニアセラミ
ックスに匹敵する程にまで強度を大幅に向上させること
ができ、２３０〜１４００ＭＰａという非常に高い曲げ
強度を示す。If the total amount of these optional components is more than 10%, the amount of apatite crystals and alkaline earth silicate crystals produced may decrease, so it is preferably 10% or less. However, if F2 is more than 5%, the glass tends to devitrify, and if Y2O3 is more than 5%, the amount of apatite crystals and alkaline earth silicate crystals produced will decrease, so F2 and Y2O3 are 5%
Limited to: And in the above crystallized glass,
Composite ceramics in which zirconia-based high-strength ceramics are dispersed can significantly improve strength to the extent that they are comparable to alumina ceramics and zirconia ceramics, and exhibit extremely high bending strength of 230 to 1400 MPa.
芯体となる複合セラミックスにおいて、結晶化ガラスが
体積百分率で５％より少ないと複合化によって生体活性
機能を付加させた効果がほとんど現れず、また、９５％
より多いと強化材としてのジルコニア系セラミックス部
分が少なくなるため、機械的強度の向上を期待できない
。よって、結晶化ガラス：ジルコニア系セラミックスの
配合比は体積百分率で５＝９５〜９５：５が好ましい。In the composite ceramic core, if the volume percentage of crystallized glass is less than 5%, the effect of adding bioactive functions due to the composite will hardly be seen;
If the amount is too large, the zirconia-based ceramic portion as a reinforcing material will be reduced, and no improvement in mechanical strength can be expected. Therefore, the mixing ratio of crystallized glass:zirconia ceramics is preferably 5=95 to 95:5 in volume percentage.
さらに、生体活性と強度の両立した材料として、とくに
好ましい範囲は、２Ｏ＋８０〜９０：１０である。Further, as a material having both bioactivity and strength, a particularly preferable range is 2O+80 to 90:10.
この複合材料に分散されるジルコニア系セラミックスは
、部分安定化ジルコニアが好ましい。部分安定化ジルコ
ニアは、Ｙ２Ｏ３、Ｍｇ２Ｏ５１Ｃａ２Ｏ５１Ｃｅ Ｏ
２のうちの１種または２種以上を固溶した正方晶ジルコ
ニア結晶の応力誘起変態を利用して高強度化をはかった
ものであり、１０００〜２Ｏ００ＭＰａもの高い曲げ強
度を示す。さらに、部分安定化ジルコニアにα−アルミ
ナを複合させると、マイクロクラッキングの効果も加わ
って１５００〜２４００ＭＰａもの強度を示す。ジルコ
ニアを部分安定化させるためには、Ｚ ｒ ０２１００
モル部に対して、モル百分率で、
Ｙ２Ｏ３： １．５〜５％
ＭｇＯ： ７〜１０％
ＣａＯニア〜１０％
ＣｅＯ２：４〜１５％
のうちの１種または２種以上を固溶させれば良い。The zirconia-based ceramic dispersed in this composite material is preferably partially stabilized zirconia. Partially stabilized zirconia is Y2O3, Mg2O51Ca2O51Ce O
The strength of this material is increased by utilizing the stress-induced transformation of a tetragonal zirconia crystal containing one or more of the following as a solid solution, and exhibits a high bending strength of 1000 to 2000 MPa. Furthermore, when alpha-alumina is combined with partially stabilized zirconia, the strength of 1500 to 2400 MPa is exhibited due to the effect of microcracking. To partially stabilize zirconia, Z r 02100
If one or more of the following is dissolved as a solid solution in terms of molar percentage based on molar parts: Y2O3: 1.5-5% MgO: 7-10% CaOnia-10% CeO2: 4-15% good.
α−アルミナを添加する場合には、部分安定化ジルコニ
ア：α−アルミナの比率は重量比で、１００：０〜１０
：９０である。これは、部分安定化ジルコニアが１０％
より少ないと、ジルコニアの応力誘起変態による強化の
効果が薄く強度の向上に効果的でないためである。さら
に、好ましい範囲は１００ ： ０〜２Ｏ ： ８０で
ある。この複合セラミックは２力月後には生体骨と化学
結合することが実、験により判明したが、ジルコニアが
複合化されているので、インブラント初期の遺骨細胞が
活発に働く時期の活性が低い。When α-alumina is added, the ratio of partially stabilized zirconia to α-alumina is 100:0 to 10 by weight.
:90. This is 10% partially stabilized zirconia.
This is because if the amount is less, the strengthening effect due to stress-induced transformation of zirconia will be weak and it will not be effective in improving the strength. Furthermore, the preferred range is 100:0 to 2O:80. Experiments have shown that this composite ceramic chemically bonds with living bone after 2 months, but because it contains zirconia, its activity is low during the early stage of implantation when skeletal cells are active.
そこで、初期の生体活性機能を向上させるために、この
複合セラミックスの表面に結晶化ガラスをコーティング
することにより初期の活性を活発化できる。このコーテ
ィング層は初期の生体活性に寄与するだけで良いので、
遺骨細胞の活発な時期（埋入後２〜４週以内）に反応す
るに十分な層の厚さがあればよい。層の厚さが１μｍ以
下では埋入後２〜３日で生体に吸収されてしまうので本
発明の目的を十分に発揮できない。また、層の厚さが１
０００μｍより厚くなると表層の結晶化ガラスの強度に
よって材料全体の強度が決ってしまうので、芯体とした
複合セラミックスの高強度性を生かすことができない。Therefore, in order to improve the initial bioactive function, the initial activity can be activated by coating the surface of this composite ceramic with crystallized glass. This coating layer only needs to contribute to initial bioactivity;
It is sufficient that the layer is thick enough to react during the active period of remains cells (within 2 to 4 weeks after implantation). If the thickness of the layer is less than 1 μm, it will be absorbed by the living body within 2 to 3 days after implantation, and the object of the present invention cannot be fully achieved. Also, the layer thickness is 1
If it is thicker than 000 μm, the strength of the entire material is determined by the strength of the crystallized glass on the surface layer, so the high strength of the composite ceramic core cannot be utilized.
したがって、コーティング層の厚さは、１〜１０００μ
ｍが好ましい。最も好ましくは、１０〜１００μｍであ
る。Therefore, the thickness of the coating layer is 1-1000μ
m is preferred. Most preferably, it is 10 to 100 μm.
上記の複合セラミックスの表面にコーティングされる結
晶化ガラスは、重量百分率で、Ｃａ２Ｏ５１２〜５６％
Ｐ２Ｏ５１〜２７％
ＳｉＯ２２２〜５０％
ＭｇＯ０〜３４％
Ａｌ２Ｏ３０〜２５％
の範囲で上記成分を含有し、ＣａＯ，Ｐ２Ｏ５、ＳｉＯ
ＭｇＯ及びＡｌｌ ２Ｏｇの含有量合計が９０％以上で
ある組成を有する生体活性の高いガラスを公知の任意手
段を用いて粉末化し、これをデイツプ、スプレー、はけ
塗りなど公知の任意手段にて塗付し、これを複合セラミ
ックスの焼成温度より低い温度で熱処理してコーティン
グすることによって製造することができる。この結晶化
ガラスは、Ｋ２Ｏ、Ｌ１２Ｏ、Ｎ ａ ２Ｏ ＳＴ ｉ
Ｏ２、ＺｒＯ５ｒＯＳＮｂ２Ｏ５、Ｔａ２Ｏ５、Ｓ
Ｂ２Ｏｓ 、Ｆ２およびＹ２Ｏ３から選ばれる少なくと
も１種を、合計量で１０％の範囲内でかつＦ２およびＹ
２Ｏ３がそれぞれ０〜５％となるように含有することが
できる。上記のガラス粉末の粒径は２Ｏ０μｍ以下であ
るのが好ましい。これは、粉末が２Ｏ０μｍ以上である
と、結晶化ガラス層に気孔が残存しやすく、その結果結
晶化ガラス層の強度が低くなり、芯体の複合セラミック
スの強度にも影響してしまうからである。しかし、粒径
が１μｍよりも小さいと、この場合にも結晶化ガラス層
に気孔が残ることがあるので、好ましくは２Ｏ０μｍが
良い。また、ガラス粉末を塗付する場合にも２Ｏ０μｍ
より細かい粒子の方が作業しやすい。このようにしてガ
ラス粉末が塗付された複合セラミックスを、複合セラミ
ックスの焼成温度と同じかそれより低い温度で熱処理す
ることによって結晶化ガラスのコーティング層が形成さ
れる。コーティングのための熱処理温度を上記の如くす
る理由は、熱処理温度が複合セラミックスの焼成温度よ
り高い場合には、芯体である複合セラミックス中の結晶
の融解などの変化が起こり、強度が低下してしまう場合
があるからである。複合セラミックス表面に均一な結晶
化ガラスのコーティング層を形成するためには、ガラス
粉末の焼結、結晶化の段階が重要である。焼結のための
熱処理は、気孔率が小さく、均一な層とするのに重要で
あり、結晶化のための熱処理は、結晶を析出させて強度
の高い層を形成するのに重要である。The crystallized glass coated on the surface of the above composite ceramic contains the above-mentioned components in the range of Ca2O512-56% P2O51-27% SiO222-50% MgO0-34% Al2O30-25%, CaO, P2O5, SiO
A highly biologically active glass having a composition in which the total content of MgO and All2Og is 90% or more is powdered using any known means, and this is coated by any known means such as dip, spray, or brush coating. It can be manufactured by attaching the composite ceramic and heat-treating it at a temperature lower than the firing temperature of the composite ceramic to coat it. This crystallized glass contains K2O, L12O, N a 2O ST i
At least one selected from O2, ZrO5rOSNb2O5, Ta2O5, S B2Os, F2 and Y2O3 in a total amount of 10% and F2 and Y2O3.
2O3 can be contained in an amount of 0 to 5%, respectively. The particle size of the above-mentioned glass powder is preferably 200 μm or less. This is because if the powder is 200 μm or more, pores tend to remain in the crystallized glass layer, resulting in a decrease in the strength of the crystallized glass layer and affecting the strength of the composite ceramic core. . However, if the particle size is smaller than 1 μm, pores may remain in the crystallized glass layer in this case as well, so 2O0 μm is preferable. Also, when applying glass powder, 2O0μm
Finer particles are easier to work with. A coating layer of crystallized glass is formed by heat-treating the composite ceramic coated with glass powder at a temperature that is the same as or lower than the firing temperature of the composite ceramic. The reason why the heat treatment temperature for coating is set as above is that if the heat treatment temperature is higher than the firing temperature of the composite ceramic, changes such as melting of the crystals in the composite ceramic core will occur, resulting in a decrease in strength. This is because it may get lost. In order to form a uniform coating layer of crystallized glass on the surface of a composite ceramic, the steps of sintering and crystallizing the glass powder are important. Heat treatment for sintering is important for forming a uniform layer with low porosity, and heat treatment for crystallization is important for precipitating crystals to form a layer with high strength.
さらに、結晶化ガラスをコートすることによって複合セ
ラミックスの表面の小さなキズ等が少なくなるので曲げ
強度はコーティングする前と同じか又はそれ以上となる
。Furthermore, by coating with crystallized glass, small scratches and the like on the surface of the composite ceramic are reduced, so that the bending strength is the same as or higher than that before coating.
前記コーティング層としては必ずしも結晶を析出させる
必要はなく、前記結晶化ガラスの結晶化前のガラス状態
であってもコーティング層が薄ければ芯体の強度への影
響はない。この場合には、コーティング用ガラスはそれ
を結晶化させたものに比べて熱膨脹係数が大きいため、
芯体を構成する複合セラミックス中の結晶化ガラスとし
て、結晶化後も熱膨脹係数の大きな組成のガラスを選ぶ
か、熱膨脹係数の小さな結晶化ガラスが選ばれた場合に
はジルコニア配合量を多くして熱膨脹係数を大きくする
必要がある。一方、コーティング層を厚くするためには
結晶化させてコーティング層の強度を向上させておく方
が好ましい。ガラス粉末の焼結温度はガラス粉末の熱収
縮測定により求められる。熱収縮の開始温度から終了温
度までが焼結温度である。また、結晶の析出温度はガラ
ス粉末の示差熱分析によって求められる。示差熱分析曲
線における発熱ピークの温度で熱処理したガラス粉末の
Ｘ線回折データを解析することにより、それぞれの発熱
ピークに対応する析出結晶を同定し、その温度から発熱
温度までをそれぞれの結晶の析出温度とする。The coating layer does not necessarily need to precipitate crystals, and even if the crystallized glass is in a glass state before crystallization, as long as the coating layer is thin, it will not affect the strength of the core. In this case, the coating glass has a larger coefficient of thermal expansion than its crystallized counterpart, so
As the crystallized glass in the composite ceramic that makes up the core, choose a glass that has a large thermal expansion coefficient even after crystallization, or if a crystallized glass that has a small thermal expansion coefficient is selected, increase the amount of zirconia mixed. It is necessary to increase the coefficient of thermal expansion. On the other hand, in order to increase the thickness of the coating layer, it is preferable to improve the strength of the coating layer by crystallizing it. The sintering temperature of the glass powder is determined by measuring the thermal shrinkage of the glass powder. The sintering temperature is the temperature from the start temperature to the end temperature of thermal contraction. Further, the crystal precipitation temperature is determined by differential thermal analysis of glass powder. By analyzing the X-ray diffraction data of glass powder heat-treated at the temperature of the exothermic peak in the differential thermal analysis curve, we can identify the precipitated crystals corresponding to each exothermic peak, and calculate the precipitation of each crystal from that temperature to the exothermic temperature. Temperature.
本発明の無機生体材料においては、複合セラミックス中
の結晶化ガラス部分とコーティングされた結晶化ガラス
層とが直接融着し、一体化するので、それらの界面の強
度が大変高いものが得られる。この接合強度を測定しよ
うとしても、結晶化ガラス部分が破壊するほど強固な接
合が得られる。In the inorganic biomaterial of the present invention, the crystallized glass portion in the composite ceramic and the coated crystallized glass layer are directly fused and integrated, so that the strength of the interface between them is extremely high. Even if an attempt is made to measure the bond strength, the bond is so strong that the crystallized glass portion is destroyed.
このコーティングのための熱処理中に熱間等方加圧（Ｈ
Ｉ Ｐ）法により、圧力をかけながら焼成すると、ガラ
スの焼結中に気孔が押しつぶされるので、気孔がほとん
ど無く、均一で強度の高いコーティング層を得ることが
できる。During the heat treatment for this coating, hot isostatic pressing (H
When the glass is fired while applying pressure using the IP method, the pores are crushed during sintering of the glass, so a uniform and strong coating layer with almost no pores can be obtained.
［実施例］
以下、実施例により本発明をさらに説明するが、本発明
はこれらの実施例に限定されるものではない。[Examples] The present invention will be further described below with reference to Examples, but the present invention is not limited to these Examples.
［実施例１］
酸化物、炭酸塩、リン酸塩、水和物、フッ化物などを原
料に用いて、表１に示す複合セラミックス用ガラスのバ
ッチを調合し、これを白金ルツボに入れて１５５０℃で
２時間溶融した。次いでガラス融液を水中に投入し、乾
燥後、ボールミルに入れて２Ｏμｍ以下の粒度に粉砕し
た。このガラス粉末を、共沈法により得られた２、５モ
ル％のＹ２Ｏ３を含むジルコニア系微粉末（平均粒径０
．３μｍ）に種々の割合で添加し、さらにボールミルを
用いて数時間湿式混合し、乾燥した。得られた混合物を
黒鉛型に入れ、３０ＭＰａの圧力をかけながら、室温か
ら１２Ｏ０℃まで一定の昇温速度３℃／分で加熱し、１
２Ｏ０℃で２時間保持して成形体の結晶化及び焼結を行
った。しかる後、炉内で室温まで冷却し、生体用複合セ
ラミックスを得た。これを３×４Ｘ３６ｍｍの角柱に切
り出し、表面を１μｍのダイヤモンド砥粒で研磨した。[Example 1] Using oxides, carbonates, phosphates, hydrates, fluorides, etc. as raw materials, a batch of glass for composite ceramics shown in Table 1 was prepared, and this was placed in a platinum crucible at 1550 °C. It was melted at ℃ for 2 hours. Next, the glass melt was poured into water, dried, and then placed in a ball mill and ground to a particle size of 20 μm or less. This glass powder was mixed with zirconia fine powder containing 2.5 mol% of Y2O3 (average particle size: 0
．． 3 μm) in various ratios, wet-mixed using a ball mill for several hours, and dried. The resulting mixture was placed in a graphite mold and heated from room temperature to 1200°C at a constant temperature increase rate of 3°C/min while applying a pressure of 30 MPa.
The molded body was crystallized and sintered by holding at 200°C for 2 hours. Thereafter, it was cooled to room temperature in a furnace to obtain composite ceramics for biological use. This was cut into a 3 x 4 x 36 mm square column, and the surface was polished with 1 μm diamond abrasive grains.
このセラミックスの三点曲げ強度を、ＪＩＳ−Ｒ１６０
１に従って測定した。The three-point bending strength of this ceramic is determined by JIS-R160.
Measured according to 1.
次に、酸化物、炭酸塩、リン酸塩、水和物、フッ化物な
どを原料に用いて、表１に示したＣａＯ−Ｐ Ｏ−８
ｉＯ系のガラスのバッチを調合し、これを白金ルツボに
入れて１５５０℃で２時間溶融した。次いでガラス融液
を水中に投入し、乾燥後、ボールミルに入れて２Ｏμｍ
以下の粒度に粉砕した。これをエタノールに分散させて
スラリー化し、このスラリーをデイツプ法により複合セ
ラミックスに塗付した。これを、１００ＭＰａの圧力を
アルゴンガスでかけながら、１１５０℃まで５°Ｃ／分
で昇温したのち１時間保持し、１０°Ｃ／分で降温して
生体用結晶化ガラスでコーティングされた複合セラミッ
クスを得た。コーティング層の厚さはデイツプ回数によ
り制御し、５０μｍとした。Next, using oxides, carbonates, phosphates, hydrates, fluorides, etc. as raw materials, the CaO-P O-8 shown in Table 1 was prepared.
A batch of iO-based glass was prepared, placed in a platinum crucible, and melted at 1550° C. for 2 hours. Next, the glass melt was poured into water, and after drying, it was put into a ball mill and made to a size of 20 μm.
It was ground to the following particle size. This was dispersed in ethanol to form a slurry, and this slurry was applied to composite ceramics by the dip method. While applying a pressure of 100 MPa with argon gas, the temperature was raised to 1150 °C at a rate of 5 °C/min, held for 1 hour, and then cooled at a rate of 10 °C/min to form a composite ceramic coated with biomedical crystallized glass. I got it. The thickness of the coating layer was controlled by the number of dips and was set to 50 μm.
表１に、芯材である複合セラミックスの母ガラス組成と
析出結晶相およびジルコニア配合量、コーティングした
生体活性結晶化ガラスの組成と析出結晶相、コーティン
グ前後の複合セラミックスの曲げ強度を示す。表１より
、このコーティングによって強度は低下しないことが判
明した。Table 1 shows the mother glass composition, precipitated crystal phase, and zirconia content of the core material composite ceramic, the composition and precipitated crystal phase of the coated bioactive crystallized glass, and the bending strength of the composite ceramic before and after coating. From Table 1, it was found that this coating did not reduce the strength.
［実施例２］
酸化物、炭酸塩、リン酸塩、水和物、フッ化物などを原
料に用いて、重量百分率で、Ｃａ ０４７．８％、Ｃｉ
０２４４．０％、Ｍｇ０１．５％、Ｐ２Ｏ５６，５％、
Ｆ２Ｏ．２％となるようにガラスのバッチを調合し、こ
れを白金ルツボに入れて１５５０°Ｃで時間溶融した。[Example 2] Using oxides, carbonates, phosphates, hydrates, fluorides, etc. as raw materials, Ca 047.8%, Ci
0244.0%, Mg01.5%, P2O56.5%,
F2O. A batch of glass was prepared at a concentration of 2%, placed in a platinum crucible, and melted at 1550°C for an hour.
次いでガラス融液を水中に投入し、乾燥後、ホールミル
に入れて２Ｏμｍ以下の粒度に粉砕した。Next, the glass melt was poured into water, dried, and then put into a hole mill and pulverized to a particle size of 20 μm or less.
このガラス粉末を、共沈法により得られた２、５モル％
のＹ２Ｏ３を含むジルコニア系微粉末（平均粒径０．３
μｍ）に添加し、さらにボールミルを用いて数時間湿式
混合し、乾燥した。なお、ガラス粉末；ジルコニア系粉
末＝１：１（体積比）となるように混合した。得られた
混合物を黒鉛型に入れ、３０ＭＰａの圧力をかけなから
、室温から１２Ｏ０℃まで一定の昇温速度３°Ｃ／分で
加熱し、１２Ｏ０℃で２時間保持して成形体の結晶化及
び焼結を行っ／
た。析出結晶はアパタイト及びウオラストナイトであっ
た。しかる後、炉内で室温まで冷却し、生体用複合セラ
ミックスを得た。これを３Ｘ４Ｘ３６闘の角柱に切り出
し、表面を１μｍのダイヤモンド砥粒て研磨した。この
セラミックスの三点曲げ強度を、ＪＩＳ−Ｒ１６０１に
従って測定したところ、７６３ＭＰａであった。これを
犬の大腿骨に埋入したところ、２週、４週後では生体活
性は十分てなく、化学的結合部分は少なかったが、８週
後には骨と化学的に結合し、生体活性であることが、病
理組織観察により確認された。2.5 mol% of this glass powder obtained by coprecipitation method
Zirconia fine powder containing Y2O3 (average particle size 0.3
μm), wet-mixed for several hours using a ball mill, and dried. The glass powder and zirconia powder were mixed in a ratio of 1:1 (volume ratio). The resulting mixture was placed in a graphite mold, heated from room temperature to 1200°C at a constant temperature increase rate of 3°C/min without applying a pressure of 30MPa, and held at 1200°C for 2 hours to crystallize the molded product. and sintering. The precipitated crystals were apatite and wollastonite. Thereafter, it was cooled to room temperature in a furnace to obtain composite ceramics for biological use. This was cut into a 3 x 4 x 36 square prism, and the surface was polished using 1 μm diamond abrasive grains. The three-point bending strength of this ceramic was measured according to JIS-R1601 and was found to be 763 MPa. When this was implanted into the femur of a dog, it was not sufficiently bioactive after 2 and 4 weeks, and there were few chemically bonded parts, but after 8 weeks it was chemically bonded to the bone and became bioactive. This was confirmed by histopathological observation.
次に、酸化物、炭酸塩、リン酸塩、水和物、フッ化物な
どを原料に用いて、重量百分率で、Ｃａ ０４７．８％
、Ｓ ｌ ０２４４．０％、Ｍｇ０１．５％、Ｐ Ｏ
６，５％、Ｆ２Ｏ．２％となるようにガラスのバッチを
調合し、これを白金ルツボに入れて１５５０°Ｃて２時
間溶融した。次いでガラス融液を水中に投入し、乾燥後
、ボールミルに入れて２Ｏμｍ以下の粒度に粉砕した。Next, using oxides, carbonates, phosphates, hydrates, fluorides, etc. as raw materials, Ca 047.8% in weight percentage
, S l 0244.0%, Mg 01.5%, P O
6.5%, F2O. A batch of glass was prepared at a concentration of 2%, placed in a platinum crucible, and melted at 1550°C for 2 hours. Next, the glass melt was poured into water, dried, and then placed in a ball mill and ground to a particle size of 20 μm or less.
これをエタノールに分散させてスラリー化し、このスラ
リーをデイツプ法により複合セラミックスに塗付した。This was dispersed in ethanol to form a slurry, and this slurry was applied to composite ceramics by the dip method.
これを、１００ＭＰａの圧力をアルゴンガスでかけなが
ら、１１５０℃まで５°Ｃ／分で昇温したのち１時間保
持し、１０℃／分で降温して生体用結晶化ガラスでコー
ティングされた複合セラミックスを得た。コーティング
層の析出結晶はアパタイト及びウオラストナイトであっ
た。コーティング層の厚さはデイツプ回数により制御し
、５０μｍとした。この試料の曲げ強度はコーティング
前とほとんど変わらず、７６０ＭＰａであった。この試
料について、犬の大腿骨に埋太し、１． ２．４．８週
後、犬を層殺し、これを取り出して病理組織観察した。While applying a pressure of 100 MPa with argon gas, the temperature was raised to 1150 °C at a rate of 5 °C/min, held for 1 hour, and then lowered at a rate of 10 °C/min to form a composite ceramic coated with biomedical crystallized glass. Obtained. The precipitated crystals in the coating layer were apatite and wollastonite. The thickness of the coating layer was controlled by the number of dips and was set to 50 μm. The bending strength of this sample was 760 MPa, almost unchanged from before coating. This sample was implanted into the femur of a dog.1. 2.4. After 8 weeks, the dogs were sacrificed and the specimens were taken out for histopathological observation.
１週後には骨形成が始まり、線維性組織が形成されずに
骨が直接インブラントに接触しはじめていた。２週で、
生体骨と完全に結合した。このコーティングにより生体
活性機能が向上したことが確認された。One week later, bone formation began, and the bone began to come into direct contact with the implant without the formation of fibrous tissue. In two weeks,
Completely integrated with living bone. It was confirmed that this coating improved the bioactive function.
［実施例３］
酸化物、炭酸塩、リン酸塩、水和物、フッ化物などを原
料に用いて、表２に示す複合セラミックス用ガラスのバ
ッチを調合し、これを白金ルツボに入れて１５５０℃で
２時間溶融した。次いでガラス融液を水中に投入し、乾
燥後、ボールミルに入れて２Ｏμｍ以下の粒度に粉砕し
た。このガラス粉末を、共沈法により得られた２、５モ
ル％のＹ２Ｏ３を含むジルコニア系微粉末（平均粒径０
．３μｍ）に種々の割合で添加し、さらにボールミルを
用いて数時間湿式混合し、乾燥した。得られた混合物を
黒鉛型に入れ、３０ＭＰａの圧力をかけながら、室温か
ら１２Ｏ０℃まで一定の昇温速度３℃／分で加熱し、１
２Ｏ０°Ｃで２時間保持して成形体の結晶化及び焼結を
行った。しかる後、炉内で室温まで冷却し、生体用複合
セラミックスを得た。これを３×４Ｘ３６ｍｍの角柱に
切り出し、表面を１μｍのダイヤモンド砥粒で研磨した
。このセラミックスの三点曲げ強度を、月５−Ｒｌ８０
１に従って測定した。[Example 3] Using oxides, carbonates, phosphates, hydrates, fluorides, etc. as raw materials, a batch of glass for composite ceramics shown in Table 2 was prepared, and this was placed in a platinum crucible at 1550 °C. It was melted at ℃ for 2 hours. Next, the glass melt was poured into water, dried, and then placed in a ball mill and ground to a particle size of 20 μm or less. This glass powder was mixed with zirconia fine powder containing 2.5 mol% of Y2O3 (average particle size: 0
．． 3 μm) in various ratios, wet-mixed using a ball mill for several hours, and dried. The resulting mixture was placed in a graphite mold and heated from room temperature to 1200°C at a constant temperature increase rate of 3°C/min while applying a pressure of 30 MPa.
The molded body was crystallized and sintered by holding at 200°C for 2 hours. Thereafter, it was cooled to room temperature in a furnace to obtain composite ceramics for biological use. This was cut into a 3 x 4 x 36 mm square column, and the surface was polished with 1 μm diamond abrasive grains. The three-point bending strength of this ceramic is 5-Rl80
Measured according to 1.
次に、酸化物、炭酸塩、リン酸塩、水和物、フッ化物な
どを原料に用いて、表２に示したＣａＯＰ２Ｏ５−８ｉ
Ｏ２系のガラスのバッチを調合し、これを白金ルツボに
入れて１５５０℃で２時間溶融した。次いでガラス融液
を水中に投入し、乾燥後、ボールミルに入れて２Ｏμｍ
以下の粒度に粉砕した。これをエタノールに分散させて
スラリー化し、このスラリーをスプレー法により複合セ
ラミックスに塗付した。これを、１００ＭＰａの圧力を
アルゴンガスでかけながら、表２に示す温度まで５℃／
分で昇温したのち１時間保持し、ガラスを焼成し１０℃
／分で降温して生体用ガラスでコーティングされた複合
セラミックスを得た。コーティング層の厚さはスプレー
時間により制御し、１０μｍとした。Next, using oxides, carbonates, phosphates, hydrates, fluorides, etc. as raw materials, CaOP2O5-8i shown in Table 2 was prepared.
A batch of O2-based glass was prepared, placed in a platinum crucible, and melted at 1550°C for 2 hours. Next, the glass melt was poured into water, and after drying, it was put into a ball mill and made to a size of 20 μm.
It was ground to the following particle size. This was dispersed in ethanol to form a slurry, and this slurry was applied to composite ceramics by a spray method. While applying a pressure of 100 MPa with argon gas, this was heated to the temperature shown in Table 2 at 5°C/
The temperature was raised for 1 minute, then held for 1 hour, and the glass was fired to 10℃.
A composite ceramic coated with biological glass was obtained by lowering the temperature at a rate of 1/min. The thickness of the coating layer was controlled by the spray time and was 10 μm.
表２に、芯材である複合セラミックスの母ガラス組成と
析出結晶相およびジルコニア配合量、コーティングした
生体活性ガラスの組成と熱処理温度、コーティング前後
の複合セラミックスの曲げ強度を示す。表２より、この
コーチインクにより強度は低下しないことが判明した。Table 2 shows the mother glass composition, precipitated crystal phase, and zirconia content of the core material composite ceramic, the composition and heat treatment temperature of the coated bioactive glass, and the bending strength of the composite ceramic before and after coating. From Table 2, it was found that this coach ink did not reduce the strength.
［実施例４］
酸化物、炭酸塩、リン酸塩、水和物、フッ化物などを原
料に用いて、重量百分率で、Ｃａ ０４７．８、Ｃｉ０
２４４．０、Ｍｇ０１．５ 、Ｐ２Ｏ５６，５、Ｆ２Ｏ
．２となるようにガラスのバッチを調合し、これを白金
ルツボに入れて１５５０°Ｃで２時間溶融した。次いて
ガラス融液を水中に投入し、乾燥後、ボールミルに入れ
て２Ｏμｍ以下の粒度に粉砕してガラス粉末を得た。こ
のカラス粉末と、共沈法により得られた２、５モル％の
Ｙ２Ｏ３を含むジルコニア系微粉末（平均粒径０．３μ
ｍ）とを、ガラス粉末：ジルコニア粉末−７：３（体積
比）で混合し、さらにボールミルを用いて数時間湿式混
合し、乾燥した。得られた混合物をパラフィンワックス
と混合した後、射出成形法により、スクリュウ付き円柱
状の人工歯根に成形した。[Example 4] Using oxides, carbonates, phosphates, hydrates, fluorides, etc. as raw materials, Ca 047.8, Ci0 in weight percentage
244.0, Mg01.5, P2O56,5, F2O
．． A batch of glass was prepared as shown in Table 2, which was placed in a platinum crucible and melted at 1550°C for 2 hours. Next, the glass melt was poured into water, dried, and then placed in a ball mill and ground to a particle size of 20 μm or less to obtain glass powder. This crow powder and zirconia fine powder (average particle size 0.3μ) containing 2.5 mol% Y2O3 obtained by coprecipitation method.
m) were mixed at a ratio of glass powder to zirconia powder of 7:3 (volume ratio), further wet-mixed using a ball mill for several hours, and then dried. The resulting mixture was mixed with paraffin wax and then molded into a cylindrical artificial tooth root with a screw by injection molding.
次にこれを脱ワツクスした後、電気炉で、１１５０°Ｃ
まで昇温しで２時間保持し、成形体の１次焼結および結
晶化を行なった。この後、断電して室温まで自然放冷し
、生体用ジルコニア強度結晶化カラスの焼結体（直径４
，５闘、全長１５ｍｍ）を得た。Next, after dewaxing this, it was heated to 1150°C in an electric furnace.
The temperature was raised to 100°C and held for 2 hours to perform primary sintering and crystallization of the molded body. After that, the power was cut off and the sintered body of bio-grade zirconia strength crystallized glass (diameter 4
, 5 fights, total length 15 mm).
さらに、上記のガラス粉末をエタノールに分散させてス
ラリー化し、このスラリーをデイツプ法によりジルコニ
ア強化結晶化ガラス焼結体の顎骨埋入部（下部末端から
８ｍｍの高さ位置まで）に塗布した。乾燥後、これを、
２Ｏ０ＭＰａの圧力をアルゴンガスでかけながら、１２
Ｏ０℃まで１０℃／分で昇温したのち１時間保持し、１
０℃／分で降温して、第１図に示すように顎骨埋入部か
生体用結晶化ガラス層１２で被覆されたジルコニア強化
結晶化ガラス１１を得た。コーティング層の厚さはデイ
ツプ回数により制御し、５０μｍとした。Furthermore, the above glass powder was dispersed in ethanol to form a slurry, and this slurry was applied to the jaw bone implantation part (up to a height of 8 mm from the lower end) of the zirconia-reinforced crystallized glass sintered body by the dip method. After drying, this
While applying a pressure of 200 MPa with argon gas,
After raising the temperature to 0°C at a rate of 10°C/min, it was held for 1 hour.
The temperature was lowered at a rate of 0° C./min to obtain a zirconia-reinforced crystallized glass 11 whose jawbone implanted portion was covered with a biomedical crystallized glass layer 12, as shown in FIG. The thickness of the coating layer was controlled by the number of dips and was set to 50 μm.
一方、酸化物、炭酸塩、リン酸塩、水和物、フッ化物な
どを原料に用いて、重量百分率で、５ｉ０６２％、ＡΩ
０ １２％、Ｎａ２Ｏ７％、に２Ｏ５％、Ｚｎ０３％
、ＣａＯ６％、Ｍｇ０３％、ＴｉＯ２２％組成となるよ
うにガラスのバッチを調合し、これを白金ルツボに入れ
て１５５０°Ｃで２時間溶融した。次いでガラス融液を
水中に投入し、乾燥後、ボールミルに入れて２Ｏμｍ以
下の粒度に粉砕した。これをエタノールと混合してスラ
リー化した。このスラリーを上記の顎骨埋入部が生体用
結晶化ガラスで被覆されたジルコニア強化結晶化ガラス
口腔内露出部にスプレーにより塗布し、十分乾燥させた
。なお、顎骨埋入部にはこのガラス粉末が塗布されない
よう可燃性のテープにより被覆しておいた。これを電気
炉中て３℃／分で昇温し、１０００℃で２時間保持して
加熱した後、炉内で自然放冷して、第１図に示すように
口腔内露出部に厚さ５０μｍの抗菌性コーティング層１
３が形成された、ジルコニア強化結晶化ガラス製人工歯
根を得た。On the other hand, using oxides, carbonates, phosphates, hydrates, fluorides, etc. as raw materials, the weight percentage is 5i062%, AΩ
0 12%, Na2O7%, 2O5%, Zn03%
A batch of glass was prepared to have a composition of , 6% CaO, 3% Mg, and 22% TiO, and this was placed in a platinum crucible and melted at 1550°C for 2 hours. Next, the glass melt was poured into water, dried, and then placed in a ball mill and ground to a particle size of 20 μm or less. This was mixed with ethanol to form a slurry. This slurry was applied by spraying to the exposed part of the oral cavity of the zirconia-reinforced crystallized glass in which the jawbone implantation part was covered with biomedical crystallized glass, and was thoroughly dried. The jawbone implantation site was covered with flammable tape to prevent the glass powder from being applied. This was heated at a rate of 3°C/min in an electric furnace, held at 1000°C for 2 hours, and then allowed to cool naturally in the furnace. 50 μm antibacterial coating layer 1
An artificial tooth root made of zirconia-reinforced crystallized glass in which No. 3 was formed was obtained.
このようにして得られた人工歯根を犬の下顎に埋入し、
１． ２．４．８週後、犬を層殺し、これを取り出して
病理組織観察した。１週後には骨形成が活発化し、２週
で、生体骨と完全に結合した。The artificial tooth root obtained in this way is implanted in the dog's lower jaw,
1. 2.4. After 8 weeks, the dogs were sacrificed and the specimens were taken out for histopathological observation. Bone formation became active after one week, and it was completely integrated with living bone in two weeks.
顎骨埋入部に生体活性な結晶化ガラスをコーティングし
たことにより、生体活性機能が向上したことが確認され
た。さらに、口腔内露出部に抗菌性ガラスをコーティン
グしたことにより、全く汚れが付着しておらず、清潔性
が保たれていた。It was confirmed that bioactive function was improved by coating the jawbone implant with bioactive crystallized glass. Furthermore, because the exposed part of the oral cavity was coated with antibacterial glass, no dirt adhered to it, and cleanliness was maintained.
［比較例］
先ず、実施例４と同様にして、ガラス粉末とジルコニア
系粉末との混合物をワックスと混合した後、射出成形法
により、スクリュウ付き円柱状の人工歯根形状に成形し
たものを得た。[Comparative Example] First, in the same manner as in Example 4, a mixture of glass powder and zirconia powder was mixed with wax, and then molded into a cylindrical artificial tooth root shape with a screw by injection molding. .
次に、これを脱ワツクスした後、ＨＩＰによって２Ｏ’
０ＭＰａの圧力をかけながら、室温から１２Ｏ０℃まで
一定の昇温速度１０°Ｃ／分で加熱し、１２Ｏ０°Ｃで
１時間保持して成形体の結晶化及び焼結を行い、円柱状
（直径４．５ ｍｍ、長さ１５ｍｍ）の生体用ジルコニ
ア強化結晶化ガラス人工歯根を得た。Next, after dewaxing this, 2O'
While applying a pressure of 0 MPa, heat from room temperature to 1200°C at a constant temperature increase rate of 10°C/min, hold at 1200°C for 1 hour to crystallize and sinter the compact, and form a cylindrical shape (diameter A living body-use zirconia-reinforced crystallized glass artificial tooth root with a diameter of 4.5 mm and a length of 15 mm was obtained.
これを犬の顎骨に埋入したところ、２週、４週後では生
体活性は十分でなく、化学的結合部分は少なかったが、
８週後には骨と化学的に結合し、生体活性であることが
、病理組織観察により確認された。また、口腔内露出部
は２週後にはうす黄色く着色し始め、４週後には約６０
μｍの厚さの黄茶色の付着物が見られた。これはＸ線回
折およびＳＥＭ観察によりポーラスなアパタイト結晶で
あることがわかり、このポーラス層に汚物が付着してい
た。When this was implanted into the jawbone of a dog, the bioactivity was not sufficient after 2 and 4 weeks, and there were few chemically bonded parts.
After 8 weeks, it was confirmed by histopathological observation that it had chemically bonded to bone and was bioactive. In addition, the exposed part of the oral cavity begins to turn pale yellow after 2 weeks, and after 4 weeks it becomes about 60% yellow.
A yellow-brown deposit with a thickness of μm was observed. This was found to be a porous apatite crystal by X-ray diffraction and SEM observation, and dirt was attached to this porous layer.
（以下余白）
［発明の効果］
本発明は、上記のように、高強度生体用複合セラミック
ス表面に生体活性の高い結晶化ガラスをコーティングす
ることによって、初期の生体活性を向上させ早期から長
期に亘って生体活性機能を発揮しつづけることを実現し
た高強度無機生体材料であり、人工骨、人工歯根用材料
として極めて有用である。(The following is a blank space) [Effects of the Invention] As described above, the present invention improves initial bioactivity and achieves long-term effects from an early stage by coating the surface of a high-strength biomedical composite ceramic with highly bioactive crystallized glass. It is a high-strength inorganic biomaterial that continues to exhibit bioactive functions over a long period of time, and is extremely useful as a material for artificial bones and artificial tooth roots.
第１図は、口腔内露出部に抗菌性コーティング層が、そ
して顎骨埋入部に生体用結晶化ガラス層が形成被覆され
た、ジルコニア強化結晶化ガラス製人工歯根の断面図で
ある。
１１・・・生体用ジルコニア強化結晶化ガラス、１２・
・・生体用結晶化ガラス層、１３・・・抗菌性コーティ
ング層。FIG. 1 is a cross-sectional view of an artificial tooth root made of zirconia-reinforced crystallized glass, in which the exposed part of the oral cavity is coated with an antibacterial coating layer, and the part embedded in the jawbone is coated with a biological glass-ceramic layer. 11... Zirconia reinforced crystallized glass for biological use, 12.
...Crystallized glass layer for biological use, 13...Antibacterial coating layer.
Claims (3)
ｉＯ＿２、ＭｇＯ及びＡｌ＿２Ｏ＿３の含有量合計が９
０％以上である組成を有する結晶化ガラス中にジルコニ
ア系セラミックスを分散させた複合セラミックスの表面
に、重量百分率で、 ＣａＯ＿５ １２〜５６％ Ｐ＿２Ｏ＿５ １〜２７％ ＳｉＯ＿２ ２２〜５０％ ＭｇＯ ０〜３４％ Ａｌ＿２Ｏ＿３ ０〜２５％ の範囲で上記成分を含有し、ＣａＯ、Ｐ＿２Ｏ＿５、Ｓ
ｉＯ＿２、ＭｇＯ及びＡｌ＿２Ｏ＿３の含有量合計が９
０％以上である組成を有するガラス又は結晶化ガラスの
コーティング層を設けたことを特徴とする無機生体材料
。(1) Contains the above components in weight percentages: CaO_5 12-56% P_2O_5 1-27% SiO_2 22-50% MgO 0-34% Al_2O_3 0-25%, CaO, P_2O_5, S
The total content of iO_2, MgO and Al_2O_3 is 9
On the surface of a composite ceramic in which zirconia ceramics are dispersed in crystallized glass having a composition of 0% or more, in weight percentages, CaO_5 12-56% P_2O_5 1-27% SiO_2 22-50% MgO 0-34% Al_2O_3 Contains the above components in the range of 0 to 25%, CaO, P_2O_5, S
The total content of iO_2, MgO and Al_2O_3 is 9
An inorganic biomaterial characterized by being provided with a coating layer of glass or crystallized glass having a composition of 0% or more.
はコーティング層中のガラスまたは結晶化ガラスがＫ＿
２Ｏ、Ｌｉ＿２Ｏ、Ｎａ＿２Ｏ、ＴｉＯ＿２、ＺｒＯ＿
２、ＳｒＯ、Ｎｂ＿２Ｏ＿５、Ｔａ＿２Ｏ＿５、Ｂ＿２
Ｏ＿３、Ｆ＿２およびＹ＿２Ｏ＿３から選ばれる少なく
とも１種を、合計量で１０％の範囲内でかつＦおよびＹ
＿２Ｏ＿３がそれぞれ０〜５％となるように含有する請
求項（１）に記載の無機生体材料。(2) The crystallized glass in the composite ceramic and/or the glass or crystallized glass in the coating layer is K_
2O, Li_2O, Na_2O, TiO_2, ZrO_
2, SrO, Nb_2O_5, Ta_2O_5, B_2
At least one selected from O_3, F_2 and Y_2O_3 in a total amount of 10% and F and Y
The inorganic biomaterial according to claim 1, containing 0 to 5% of _2O_3.
いた人工歯根または人工骨。(3) An artificial tooth root or artificial bone using the inorganic biomaterial according to claim (1) or (2).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2248348A JPH04126157A (en) | 1990-09-18 | 1990-09-18 | Inorganic biomaterial |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2248348A JPH04126157A (en) | 1990-09-18 | 1990-09-18 | Inorganic biomaterial |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04126157A true JPH04126157A (en) | 1992-04-27 |
Family
ID=17176759
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2248348A Pending JPH04126157A (en) | 1990-09-18 | 1990-09-18 | Inorganic biomaterial |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04126157A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE112011100008T5 (en) | 2010-04-06 | 2012-06-28 | Nec Tokin Corp. | Electric storage device |
| JP2014512325A (en) * | 2011-04-05 | 2014-05-22 | アールイージー ４ ライフ リジェネレーション テクノロジー， ソシエダッド アノニマ | Bioactive glass composition, method for preparing the same, method for producing the same, and glass raw material |
-
1990
- 1990-09-18 JP JP2248348A patent/JPH04126157A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE112011100008T5 (en) | 2010-04-06 | 2012-06-28 | Nec Tokin Corp. | Electric storage device |
| JP2014512325A (en) * | 2011-04-05 | 2014-05-22 | アールイージー ４ ライフ リジェネレーション テクノロジー， ソシエダッド アノニマ | Bioactive glass composition, method for preparing the same, method for producing the same, and glass raw material |
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