JPH02209148A - Artificial bone, artificial tooth, bone fixing screw and its production - Google Patents
Artificial bone, artificial tooth, bone fixing screw and its productionInfo
- Publication number
- JPH02209148A JPH02209148A JP1027652A JP2765289A JPH02209148A JP H02209148 A JPH02209148 A JP H02209148A JP 1027652 A JP1027652 A JP 1027652A JP 2765289 A JP2765289 A JP 2765289A JP H02209148 A JPH02209148 A JP H02209148A
- Authority
- JP
- Japan
- Prior art keywords
- bone
- artificial
- calcium phosphate
- fixing screw
- phosphate compound
- 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.)
- Granted
Links
- 210000000988 bone and bone Anatomy 0.000 title claims abstract description 106
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 19
- 239000001506 calcium phosphate Substances 0.000 claims abstract description 61
- 229910000389 calcium phosphate Inorganic materials 0.000 claims abstract description 58
- 235000011010 calcium phosphates Nutrition 0.000 claims abstract description 58
- 229920005613 synthetic organic polymer Polymers 0.000 claims abstract description 27
- 239000002344 surface layer Substances 0.000 claims abstract description 23
- 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 abstract description 17
- 239000000178 monomer Substances 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 7
- -1 calcium phosphate compound Chemical class 0.000 claims description 60
- 238000000034 method Methods 0.000 claims description 11
- 210000001519 tissue Anatomy 0.000 claims description 10
- 239000000203 mixture Substances 0.000 abstract description 6
- 238000004381 surface treatment Methods 0.000 abstract description 5
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 31
- 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 31
- 238000002156 mixing Methods 0.000 description 13
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 10
- 239000004926 polymethyl methacrylate Substances 0.000 description 10
- 239000002131 composite material Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 238000009832 plasma treatment Methods 0.000 description 7
- 238000012545 processing Methods 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 239000012890 simulated body fluid Substances 0.000 description 6
- 239000000853 adhesive Substances 0.000 description 5
- 230000001070 adhesive effect Effects 0.000 description 5
- 239000003607 modifier Substances 0.000 description 5
- 230000011164 ossification Effects 0.000 description 5
- 238000005520 cutting process Methods 0.000 description 4
- 239000010409 thin film Substances 0.000 description 4
- 150000008064 anhydrides Chemical class 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- GBNXLQPMFAUCOI-UHFFFAOYSA-H tetracalcium;oxygen(2-);diphosphate Chemical compound [O-2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GBNXLQPMFAUCOI-UHFFFAOYSA-H 0.000 description 3
- 210000002303 tibia Anatomy 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
- 208000018035 Dental disease Diseases 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- 206010028980 Neoplasm Diseases 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 208000014151 Stomatognathic disease Diseases 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000009750 centrifugal casting Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 229910003460 diamond Inorganic materials 0.000 description 2
- 239000010432 diamond Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052587 fluorapatite Inorganic materials 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 208000014674 injury Diseases 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000001356 surgical procedure Methods 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 230000008733 trauma Effects 0.000 description 2
- PREIHGSIAPRHNC-UHFFFAOYSA-N 10-dihydroxyphosphinothioyloxydecyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCCCCCCCOP(O)(O)=S PREIHGSIAPRHNC-UHFFFAOYSA-N 0.000 description 1
- QTKPMCIBUROOGY-UHFFFAOYSA-N 2,2,2-trifluoroethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(F)(F)F QTKPMCIBUROOGY-UHFFFAOYSA-N 0.000 description 1
- RMCCONIRBZIDTH-UHFFFAOYSA-N 2-(2-methylprop-2-enoyloxy)ethyl 1,3-dioxo-2-benzofuran-5-carboxylate Chemical compound CC(=C)C(=O)OCCOC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 RMCCONIRBZIDTH-UHFFFAOYSA-N 0.000 description 1
- SEILKFZTLVMHRR-UHFFFAOYSA-N 2-phosphonooxyethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOP(O)(O)=O SEILKFZTLVMHRR-UHFFFAOYSA-N 0.000 description 1
- GOGCLLMDQOJKHB-UHFFFAOYSA-N 4-[2-(2-methylprop-2-enoyloxy)ethoxycarbonyl]phthalic acid Chemical compound CC(=C)C(=O)OCCOC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 GOGCLLMDQOJKHB-UHFFFAOYSA-N 0.000 description 1
- IRQWEODKXLDORP-UHFFFAOYSA-N 4-ethenylbenzoic acid Chemical compound OC(=O)C1=CC=C(C=C)C=C1 IRQWEODKXLDORP-UHFFFAOYSA-N 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- 229920000954 Polyglycolide Polymers 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- JUNWLZAGQLJVLR-UHFFFAOYSA-J calcium diphosphate Chemical compound [Ca+2].[Ca+2].[O-]P([O-])(=O)OP([O-])([O-])=O JUNWLZAGQLJVLR-UHFFFAOYSA-J 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 229940043256 calcium pyrophosphate Drugs 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 235000019821 dicalcium diphosphate Nutrition 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002504 physiological saline solution Substances 0.000 description 1
- 229920000747 poly(lactic acid) Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000004633 polyglycolic acid Substances 0.000 description 1
- 239000004626 polylactic acid Substances 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 239000011265 semifinished product Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
- A61B17/00—Surgical instruments, devices or methods, e.g. tourniquets
- A61B17/56—Surgical instruments or methods for treatment of bones or joints; Devices specially adapted therefor
- A61B17/58—Surgical instruments or methods for treatment of bones or joints; Devices specially adapted therefor for osteosynthesis, e.g. bone plates, screws, setting implements or the like
- A61B17/68—Internal fixation devices, including fasteners and spinal fixators, even if a part thereof projects from the skin
- A61B17/84—Fasteners therefor or fasteners being internal fixation devices
- A61B17/86—Pins or screws or threaded wires; nuts therefor
- A61B17/866—Material or manufacture
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
- A61F2/00—Filters implantable into blood vessels; Prostheses, i.e. artificial substitutes or replacements for parts of the body; Appliances for connecting them with the body; Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
- A61F2/0077—Special surfaces of prostheses, e.g. for improving ingrowth
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、腫瘍摘出や外傷により失われた骨組織を修復
治療するための人工骨、歯牙疾患等により失われた歯を
修復治療するための人工歯及び骨と骨との接合や骨と硬
組織代替材料等の接合に使用する固定用ねじに関する。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to artificial bone for restoring bone tissue lost due to tumor removal or trauma, and for restoring teeth lost due to dental disease. This invention relates to artificial teeth and fixation screws used to connect bones to bones, bones to hard tissue substitute materials, etc.
従来から、腫瘍摘出や外傷により失われた骨組織を修復
治療するための人工骨、歯牙疾患等により失われた歯を
修復治療するための人工歯及び骨と骨との接合や骨と硬
組織代替材料等の接合に使用する固定用ねじ自体は公知
である。しかし、人工骨及び人工歯として従来使用され
ているセラミックス材料は、加工が困難であり、更１こ
、硬すぎるという欠点を有している。これらの欠点を解
決するため、リン酸カルシウム化合物１０〜９０重量％
及び合成有機重合体９０〜１０重量％を含有する人工骨
及び人工歯（例えば、同一出願人の特公昭６３−４４３
７９号公報等）並びに骨及び硬組織代替材の固定用ねじ
（例えば、同じく、同一出願人の特開昭６２−２６８５
５３号公報等）が開発されている。これらの人工骨、人
工歯並びに骨及び硬組織代替材の固定用ねじけ、生体適
合性に優れ、骨及び歯牙と同程度の強度及び靭性を有し
、更に加工性にも富んでいる。Conventionally, artificial bones are used to repair bone tissue lost due to tumor removal or trauma, artificial teeth are used to repair teeth lost due to dental disease, etc., and bone-to-bone bonding and bone-to-hard tissue are used. Fixing screws themselves used for joining alternative materials are well known. However, ceramic materials conventionally used for artificial bones and teeth have the disadvantage that they are difficult to process and are too hard. In order to solve these drawbacks, calcium phosphate compound 10-90% by weight
and artificial bones and teeth containing 90 to 10% by weight of synthetic organic polymers (for example, Japanese Patent Publication No. 63-443 of the same applicant)
No. 79, etc.) and screws for fixing bone and hard tissue substitutes (for example, Japanese Patent Laid-Open No. 62-2685, also filed by the same applicant).
No. 53, etc.) have been developed. These screws for fixing artificial bones, artificial teeth, and bone and hard tissue substitutes have excellent biocompatibility, have strength and toughness comparable to bones and teeth, and are also highly workable.
しかしながら、これらの従来技術による人工骨。However, these conventional artificial bones.
人工歯及び固定用ねじの場合には、その表層部における
リン酸カルシウム化合物の露出量は、わずかであり、従
って、リン酸カルシウム化合物の緻密体と比較すると表
層部の生体親和性が乏しいという欠点がある。又、リン
酸カルシウム化合物の露出量を増加させるために、原料
として使用するリン酸カルシウム化合物の混合比を増加
すると、人工骨等の加工性が悪くなり、安定した製造は
不可能である。In the case of artificial teeth and fixation screws, the amount of calcium phosphate compound exposed in the surface layer thereof is small, and therefore the surface layer has a disadvantage of poor biocompatibility compared to a dense body of calcium phosphate compound. Furthermore, if the mixing ratio of the calcium phosphate compound used as a raw material is increased in order to increase the exposed amount of the calcium phosphate compound, the processability of the artificial bone etc. will deteriorate, making stable production impossible.
更に、これらの従来技術においては、加熱重合後に、旋
盤等を使用して所望の形状に加工することにより、切削
に伴い発熱が生じ合成有機重合体が溶融し、その結果と
して、人工骨等の表層部を重合体薄膜が被覆してしまう
という欠点がある。Furthermore, in these conventional techniques, after heating and polymerizing, the synthetic organic polymer is processed into the desired shape using a lathe, etc., which generates heat during cutting and melts the synthetic organic polymer. There is a drawback that the surface layer portion is covered with a thin polymer film.
従って生体親和性を向上させるために１本来表層部に露
出すべきリン酸カルシウム化合物が露出していないのが
実状である。Therefore, the actual situation is that the calcium phosphate compound, which should originally be exposed on the surface layer in order to improve biocompatibility, is not exposed.
そこで１本発明の主要な目的は、生体親和性に富む人工
骨、人工歯及び骨固定用ねじ並びにその製造方法を提供
することである。Therefore, one main object of the present invention is to provide an artificial bone, an artificial tooth, a screw for bone fixation, and a method for manufacturing the same, which are highly biocompatible.
本発明の別の目的は、人工骨等が容易に製造できる範囲
内のリン酸カルシウム化合物及び合成有機重合体の混合
割合であり、しかも製造した人工骨等の表層部には顕著
な生体親和性を示すために十分な面積比のリン酸カルシ
ウム化合物が露出する人工骨１人工歯及び骨固定用ねじ
並びにその製造方法を提供することである。Another object of the present invention is to find a mixing ratio of a calcium phosphate compound and a synthetic organic polymer that is within a range that allows for easy production of artificial bones, etc., and which exhibits remarkable biocompatibility in the surface layer of the produced artificial bones. An object of the present invention is to provide an artificial bone (1) in which a calcium phosphate compound is exposed in a sufficient area ratio, an artificial tooth, a bone fixing screw, and a method for manufacturing the same.
本発明の更に別の目的は、加工により、−時的に合成有
機重合体薄膜にて被覆された場合であっても、容易に十
分な面積比のリン酸カルシウム化合物を露出させること
ができ、従って、生体親和性を損なうことのない人工骨
、人工歯及び骨固定用ねじ並びにその製造方法を提供す
ることである。Yet another object of the present invention is that processing can easily expose a sufficient area ratio of the calcium phosphate compound, even when occasionally coated with a thin film of synthetic organic polymer; An object of the present invention is to provide an artificial bone, an artificial tooth, a bone fixing screw, and a method for producing the same without impairing biocompatibility.
本発明によれば、リン酸カルシウム化合物４０〜９５重
量％と、合成有機重合体６０〜５重量％とを含有する人
工骨、人工歯及び骨固定用ねじであって、生体組織と接
触する表層部にリン酸カルシウム化合物を面積比で５０
％以上露出させることを特徴とする人工骨、人工歯及び
骨固定用ねじが提供される。According to the present invention, there is provided an artificial bone, an artificial tooth, and a bone fixing screw containing 40 to 95% by weight of a calcium phosphate compound and 60 to 5% by weight of a synthetic organic polymer. Calcium phosphate compound in area ratio of 50
Provided are artificial bones, artificial teeth, and bone fixing screws that are characterized by exposing at least %.
更に、本発明によれば、人工骨、人工歯及び骨固定用ね
じを製造するにあたり、リン酸カルシウム化合物及び合
成有機重合体の原料モノマーを混合し、次いで加熱、重
合した後に、所望の形状に加工し、更に表層部に表面処
理を施すことによりリン酸カルシウム化合物を露出させ
ることを特徴とする人工骨、人工歯及び骨固定用ねじの
製造方法が提供される。Further, according to the present invention, in manufacturing artificial bones, artificial teeth, and bone fixing screws, raw material monomers of a calcium phosphate compound and a synthetic organic polymer are mixed, then heated and polymerized, and then processed into a desired shape. Furthermore, there is provided a method for manufacturing an artificial bone, an artificial tooth, and a bone fixing screw, which comprises exposing the calcium phosphate compound by subjecting the surface layer to a surface treatment.
以下本発明を更に詳細に説明する。The present invention will be explained in more detail below.
本発明の人工骨、人工歯及び骨固定用ねじは、リン酸カ
ルシウム化合物と、合成有機重合体とを特定量含有し、
生体組織と接触する表層部には、リン酸カルシウム化合
物を面積比で特定量以上露出させることを特徴とする。The artificial bone, artificial tooth, and bone fixing screw of the present invention contain a specific amount of a calcium phosphate compound and a synthetic organic polymer,
It is characterized in that a calcium phosphate compound is exposed in an area ratio of a specific amount or more on the surface layer that comes into contact with living tissue.
本発明においてリン酸カルシウム化合物としては、リン
酸三カルシウム、ヒドロキシアパタイト、リン酸四カル
シウム、オキシアパタイト、ピロリン酸カルシウム、フ
ッ素アパタイト、ヒドロキシアパタイトの水酸基の一部
がフッ素イオンで置換された化合物又はこれらの混合物
等を挙げることができ、特に新生骨の生成速度が早いリ
ン酸三カルシウム、ヒドロキシアパタイト、リン酸四カ
ルシウム及びフッ素アパタイト等から選択される１種又
は２種以上の混合物を使用することが好ましい、更にま
た新生骨の生成速度が最も早いヒドロキシアパタイトを
リン酸カルシウム化合物として使用するのが最も好まし
い。ヒドロキシアパタイトの中でも、５００’Ｃ以上、
特に好ましくは７００℃以上で熱処理して得たヒドロキ
シアパタイトが特に新生骨の生成が早く好ましい。熱処
理の上限温度については特に限定されるものではないが
、ヒドロキシアパタイトが分解を開始するので、分解温
度以下とすべきである。In the present invention, the calcium phosphate compound includes tricalcium phosphate, hydroxyapatite, tetracalcium phosphate, oxyapatite, calcium pyrophosphate, fluoroapatite, a compound in which a part of the hydroxyl group of hydroxyapatite is replaced with fluorine ions, or a mixture thereof. In particular, it is preferable to use one type or a mixture of two or more types selected from tricalcium phosphate, hydroxyapatite, tetracalcium phosphate, fluoroapatite, etc., which have a high rate of new bone formation. Furthermore, it is most preferable to use hydroxyapatite, which produces the fastest new bone, as the calcium phosphate compound. Among hydroxyapatite, 500'C or more,
Particularly preferably, hydroxyapatite obtained by heat treatment at 700° C. or higher is particularly preferred because new bone formation is quick. The upper limit temperature of the heat treatment is not particularly limited, but since hydroxyapatite starts to decompose, it should be lower than the decomposition temperature.
本発明において好ましく使用できるリン酸カルシウム化
合物は、湿式法、乾式法又は水熱法等の公知の製造方法
により、人工的に合成されたものであっても、または骨
等から得られる天然のものであっても共に使用できる。Calcium phosphate compounds that can be preferably used in the present invention may be artificially synthesized by known production methods such as wet, dry, or hydrothermal methods, or natural ones obtained from bones, etc. Can also be used together.
更に、本発明において好ましく使用できるリン酸カルシ
ウム化合物は、合成有機重合体上ツマ−との混合が可能
である限りは粉末状、顆粒状のいずれであっても好まし
く使用できる。Furthermore, the calcium phosphate compound that can be preferably used in the present invention can be preferably used in either powder or granule form as long as it can be mixed with the synthetic organic polymer.
本発明においては、前記リン酸カルシウム化合物の表面
を、予め改質しておくことが好ましい。In the present invention, it is preferable that the surface of the calcium phosphate compound is modified in advance.
該改質処理を行うことにより１人工骨、人工歯及び骨固
定用ねじの強度を増加させることができ、生理食塩水中
の長期間浸漬において強度劣化を防止することができる
。更に、表面改質したリン酸カルシウム化合物を使用す
ることにより、合成有機重合体との親和性が著しく向上
し１人工骨等の製造にあたっての原料混合時にも、特別
な混合法や熟練等を必要とせず、容易に均一混合が可能
になる。By performing this modification treatment, the strength of the artificial bone, artificial tooth, and bone fixing screw can be increased, and deterioration in strength can be prevented during long-term immersion in physiological saline. Furthermore, by using a surface-modified calcium phosphate compound, its affinity with synthetic organic polymers is significantly improved, and special mixing methods and skills are not required when mixing raw materials for manufacturing artificial bones. , uniform mixing is easily possible.
前記リン酸カルシウム化合物の表面を改質するための改
質剤としては１例えば、４−メタクリロイルオキシエト
キシカルボニルフタル酸（以下、４−ＭＥＣＰと称する
）、４−メタクリロイルオキシエトキシカルボニルフタ
ル酸無水物（以下。Examples of the modifier for modifying the surface of the calcium phosphate compound include 4-methacryloyloxyethoxycarbonylphthalic acid (hereinafter referred to as 4-MECP) and 4-methacryloyloxyethoxycarbonylphthalic anhydride (hereinafter referred to as 4-MECP).
４−ＭＥＣＰＡと称する）、ｐ−ビニル安息香酸等の不
飽和ポリカルボン酸及びその無水物；２−メタクリロイ
ルオキシエチルホスフェート等の不飽和ポリリン酸及び
その無水物；１０−メタクリロイルオキシデシルチオホ
スフェート等の不飽和ポリチオリン酸及びその無水物等
を好ましく挙げることができる。前記改質剤の中では、
４−ＭＥＣＰＡ、４−ＭＥＣＰは少量でリン酸カルシウ
ム化合物の表面を改質できるため、特に好ましい。4-MECPA), unsaturated polycarboxylic acids and their anhydrides such as p-vinylbenzoic acid; unsaturated polyphosphoric acids and their anhydrides such as 2-methacryloyloxyethyl phosphate; 10-methacryloyloxydecyl thiophosphate, etc. Preferred examples include unsaturated polythiophosphoric acid and its anhydride. Among the modifiers,
4-MECPA and 4-MECP are particularly preferred because they can modify the surface of the calcium phosphate compound with a small amount.
改質剤の使用量は、リン酸カルシウム化合物と合成有機
重合体の原料モノマーとの親・相性が向上し、人工骨等
の製造にあたっての原料混合時に容易に均一に混合でき
、更に、人工骨等の強度の劣化を防止できるように、リ
ン酸カルシウム化合物の表面を改質できる量を使用する
ことが好ましい。The amount of modifier used is determined by improving the affinity and compatibility between the calcium phosphate compound and the raw material monomer of the synthetic organic polymer, allowing for easy and uniform mixing of raw materials for the production of artificial bones, etc. It is preferable to use an amount that can modify the surface of the calcium phosphate compound so as to prevent deterioration of strength.
かかる量は、特に限定はされるものではないが、例えば
、リン酸カルシウム化合物１００重量部に対して、０．
０５重量部以上、特に好ましくは０．１〜０．５重量部
使用することが望ましい。This amount is not particularly limited, but for example, 0.00 parts by weight per 100 parts by weight of the calcium phosphate compound.
It is desirable to use 0.05 parts by weight or more, particularly preferably 0.1 to 0.5 parts by weight.
この場合に最も高強度の人工骨等が製造できる。In this case, the highest strength artificial bone etc. can be manufactured.
また前記改質剤の量を増加することは、もちろん可能で
あるが、経済性及び生体親和性の観点からは、２．０重
量部以下が好ましい。Although it is of course possible to increase the amount of the modifier, from the viewpoint of economy and biocompatibility, it is preferably 2.0 parts by weight or less.
改質方法もリン酸カルシウム化合物の表面を改質し得る
かぎり、任意の方法が使用できる。例えば、メタクリル
酸メチル、メタクリル酸トリフルオロエチル等の合成有
機重合体のモノマー、アセトン等の溶媒に改質剤を溶解
し、次いで、リン酸カルシウム化合物を投入し、３〜１
０分間撹拌後、リン酸カルシウム化合物の沈殿物を自然
乾燥又は加熱乾燥する方法により改質できる。Any modification method can be used as long as the surface of the calcium phosphate compound can be modified. For example, a modifier is dissolved in a synthetic organic polymer monomer such as methyl methacrylate or trifluoroethyl methacrylate, or a solvent such as acetone, and then a calcium phosphate compound is added to
After stirring for 0 minutes, the precipitate of the calcium phosphate compound can be modified by air drying or heating drying.
本発明において好ましく使用できる有機重合体としては
、生体に対し毒性がなく、且つリン酸カルシウム化合物
との親和性があれば特に限定されず１例えば、ポリ乳酸
ポリグリコール酸等のカルボン酸系重合体；ポリメタク
リル酸メチル（以下、ＰＭＭＡと称す）、ポリ（メタク
リル酸トリフルオロエチル）（以下、ＰＴＦＥＭＡと称
す）等のカルボン酸エステル系重合体；及びポリエチレ
ン（以下、ＰＥと称す）、ポリプロピレン等のオレフィ
ン系重合体が好ましく使用できる。これらの重合体のう
ちでは、強度及びリン酸カルシウム化合物との親和性が
高いという観点から、特に、ＰＭＭＡ及びＰＴＦＥＭＡ
が好ましい。これらの合成有機重合体は、いずれも公知
の方法にて製造される重合体が好ましく使用できる。Organic polymers that can be preferably used in the present invention are not particularly limited as long as they are non-toxic to living organisms and have an affinity for calcium phosphate compounds.For example, carboxylic acid polymers such as polylactic acid and polyglycolic acid; Carboxylic acid ester-based polymers such as methyl methacrylate (hereinafter referred to as PMMA) and poly(trifluoroethyl methacrylate) (hereinafter referred to as PTFEMA); and olefin-based polymers such as polyethylene (hereinafter referred to as PE) and polypropylene. Polymers can be preferably used. Among these polymers, PMMA and PTFEMA are particularly preferred from the viewpoint of strength and high affinity with calcium phosphate compounds.
is preferred. As these synthetic organic polymers, polymers produced by known methods can be preferably used.
本発明において、リン酸カルシウム化合物及び合成有機
重合体との配合割合は、リン酸カルシウム化合物４０〜
９５重量％、好ましくは５０〜８５重量％、合成有機重
合体６０〜５重量％、好ましくは５０〜１５重量％であ
る。In the present invention, the blending ratio of the calcium phosphate compound and the synthetic organic polymer is 40 to 40%.
95% by weight, preferably 50-85% by weight, synthetic organic polymer 60-5% by weight, preferably 50-15% by weight.
リン酸カルシウム化合物の量が、４０重量％未満である
と、加工後に表面処理を施しても表層部に面積比で５０
％以上のリン酸カルシウム化合物を露出させることがで
きず、従って、十分な生体適合性を有する人工骨、人工
歯及び骨固定用ねじを製造することが困難である。又、
リン酸カルシウム化合物の量が、９５重景％を超えると
、人工骨、人工歯及び骨固定用ねじの加工が困難になる
。If the amount of calcium phosphate compound is less than 40% by weight, even if surface treatment is performed after processing, 50%
Therefore, it is difficult to produce artificial bones, artificial teeth, and bone fixation screws with sufficient biocompatibility. or,
If the amount of the calcium phosphate compound exceeds 95%, it becomes difficult to process artificial bones, artificial teeth, and screws for bone fixation.
本発明による人工骨１人工歯及び骨固定用ねじは、好ま
しくは、リン酸カルシウム化合物の粉末又は顆粒並びに
合成有機重合体のモノマーとを撹拌混合し、その後、好
ましくは４０〜１００℃で１〜１０時間段階的に加熱重
合することによって製造できる。この場合、人工骨、人
工歯及び骨固定用ねじの外周部にリン酸カルシウム化合
物を多く含有させるために、遠心鋳造法を使用して製造
することが好ましい、しかし、遠心鋳造法を使用した場
合に、常にリン酸カルシウム化合物が露出するという保
証は存在しない。Artificial bone 1 According to the present invention, the artificial tooth and bone fixing screw are prepared by stirring and mixing powder or granules of a calcium phosphate compound and a monomer of a synthetic organic polymer, and then preferably at 40 to 100°C for 1 to 10 hours. It can be produced by stepwise heating polymerization. In this case, in order to contain a large amount of calcium phosphate compound in the outer periphery of the artificial bone, artificial tooth, and bone fixation screw, it is preferable to manufacture using the centrifugal casting method. However, when using the centrifugal casting method, There is no guarantee that calcium phosphate compounds will always be exposed.
本発明の人工骨、人工歯及び骨固定用ねじの製造にあた
っては、前記重合後、所望の形状に加工するために、例
えば、旋盤、ダイヤモンドカッター、ダイヤモンドディ
スク等により、容易に加工することができる。これは、
本発明に用いる材料が靭性及び加工性に優れているため
である。In manufacturing the artificial bone, artificial tooth, and bone fixing screw of the present invention, after the polymerization, processing can be easily performed using, for example, a lathe, a diamond cutter, a diamond disk, etc., in order to process it into a desired shape. . this is,
This is because the material used in the present invention has excellent toughness and workability.
本発明の人工骨、人工歯及び骨固定用ねじの製造におい
ては、更に、人工骨、人工歯及び骨固定用ねじの表面の
処理を行う。表面処理は、好ましくは、例えば、旋盤等
による加工後の半製品である人工骨等を、少なくともカ
ルシウムイオン及びリンイオンを含有する溶液中に浸漬
して行う。この処理により、人工骨等表面に最初から露
出しているリン酸カルシウム化合物を核として、該核に
エピタキシャル成長が起こり、リン酸カルシウム化合物
が析出し、表層部を覆う、このようにして、当初の混合
時には、期待し得ない程の広い面積にリン酸カルシウム
化合物を露出させることが可能となる。In manufacturing the artificial bone, artificial tooth, and bone fixing screw of the present invention, the surfaces of the artificial bone, artificial tooth, and bone fixing screw are further treated. The surface treatment is preferably performed, for example, by immersing the artificial bone, which is a semi-finished product after processing using a lathe or the like, in a solution containing at least calcium ions and phosphorus ions. Through this treatment, epitaxial growth occurs in the core of the calcium phosphate compound that is exposed from the beginning on the surface of the artificial bone, etc., and the calcium phosphate compound precipitates and covers the surface layer. This makes it possible to expose the calcium phosphate compound over a wider area than previously possible.
本発明の人工骨、人工歯及び骨固定用ねじの製造におい
ては、加工時の切削による熱のために。In manufacturing the artificial bones, artificial teeth, and bone fixation screws of the present invention, due to the heat generated by cutting during processing.
耐熱性の低い合成有機重合体が表層部を薄く被覆する場
合があるが、かかる場合には、例えば、プラズマ処理を
行うことにより、合成有機重合体薄膜を飛ばし、リン酸
カルシウム化合物を露出させることができる。この際、
切削加工時に薄膜で被覆されたリン酸カルシウム化合物
のみでなく、切削加工時には、表面にまで達していない
比較的浅い位置に存在するリン酸カルシウム化合物まで
をも露出させることが可能である。この場合にも。There are cases where the surface layer is thinly coated with a synthetic organic polymer with low heat resistance; in such cases, for example, plasma treatment can be performed to remove the synthetic organic polymer thin film and expose the calcium phosphate compound. . On this occasion,
It is possible to expose not only the calcium phosphate compound coated with a thin film during the cutting process, but also the calcium phosphate compound present at a relatively shallow position that does not reach the surface. Also in this case.
当初の混合時には、期待し得ない程の広い面積にリン酸
カルシウム化合物を露出させることが可能となる。なお
、前記プラズマ処理によって、表面が活性化され、その
結果として生体活性が向上する場合もある。During initial mixing, it is possible to expose a larger area of calcium phosphate compound than would be expected. Note that the plasma treatment may activate the surface and improve bioactivity as a result.
当然ながら、前記の溶液浸漬処理及びプラズマ処理を組
合せて実施することにより、効果は相乗的に増大する。Naturally, by performing the solution immersion treatment and the plasma treatment in combination, the effect increases synergistically.
本発明の人工骨、人工歯及び骨固定用ねじにおいて１表
層部に露出させるリン酸カルシウム化合物の面積比は、
５０％以上が好ましく、特に６０％以上、更に好ましく
は７０％以上が望ましい。In the artificial bone, artificial tooth, and bone fixing screw of the present invention, the area ratio of the calcium phosphate compound exposed in one surface layer is:
It is preferably 50% or more, particularly 60% or more, and even more preferably 70% or more.
その理由は、本発明の人工骨、人工歯及び骨固定用ねじ
においては、５０％未満であっても生体親和性において
問題は生じない場合もあるが、リン酸カルシウム化合物
単独の人工骨、人工歯及び骨固定用ねじと全く遜色のな
い骨との接着力を持たせるためには、５０％以上のリン
酸カルシウム化合物の露出が必要なためである。The reason for this is that in the artificial bones, artificial teeth, and bone fixing screws of the present invention, there may be no problem in terms of biocompatibility even if the concentration is less than 50%; This is because 50% or more of the calcium phosphate compound needs to be exposed in order to have adhesion strength to bone that is comparable to that of bone fixation screws.
本発明の人工骨、人工歯及び骨固定用ねじの物性を実際
の骨に可能な限り近似させるために、又生体にインブラ
ントした場合の安全性のために、より高強度且つ高靭性
とするには、人工骨等の中心部に金属棒又は板を挿入す
ることが好ましい。In order to make the physical properties of the artificial bones, artificial teeth, and bone fixing screws of the present invention as close as possible to those of actual bones, and for safety when implanted in a living body, they are made to have higher strength and toughness. For this purpose, it is preferable to insert a metal rod or plate into the center of the artificial bone or the like.
この場合の金属は、前記目的に合致する限り特に限定は
されないが、リン酸カルシウム化合物と合成有機重合体
との複合体に何等かの原因でクラック等が生じる場合も
考えられるため、毒性が少ない又は無いといわれるステ
ンレス（３１６Ｌ）やチタンを使用することが好ましい
、中心部に金属を入れる場合、その外側に金属が露出し
ないように挿入することが好ましい。金属との接着には
接着剤を使用してよいが、所望の初期接着強度が得られ
る限りは接着剤の種類は限定されない１本発明によるリ
ン酸カルシウム化合物と合成有機重合体との複合体は、
金属値の接着性が他の材料と比較して良好であり、且つ
靭性が高いため曲げやねじれによってもクラックが入り
にくい。The metal in this case is not particularly limited as long as it meets the above purpose, but since cracks may occur for some reason in the composite of the calcium phosphate compound and the synthetic organic polymer, metals with low or no toxicity may be used. It is preferable to use stainless steel (316L) or titanium.When inserting metal in the center, it is preferable to insert it so that the metal is not exposed on the outside. An adhesive may be used for adhesion to the metal, but the type of adhesive is not limited as long as the desired initial adhesive strength is obtained.1 The composite of the calcium phosphate compound and synthetic organic polymer according to the present invention is:
It has good adhesion to metals compared to other materials, and has high toughness, so it is difficult to crack even when bent or twisted.
本発明の固定用ねじの形状は、固定ができるものであれ
ば特に限定されるものではないが、例えば、第１図に示
すように、ねじ１０の頭１１が多角形でレンチまたはス
パナ−でねじ込みが可能であり、ねじの全長にわたりね
じ山１２が切っであるもの、第２図に示すように、ねじ
２０の一部のみに、ねじ山２２が切ってあり、ドライバ
ーによりねじ込みが可能なように頭２１に溝２３が切っ
であるもの、更には、第３図に示すボルト３１とナツト
３２とからなるねじ３０等を挙げることができる。The shape of the fixing screw of the present invention is not particularly limited as long as it can be fixed, but for example, as shown in FIG. Threads that can be screwed in and have threads 12 cut along the entire length of the screw, and screws that have threads 22 cut only on a part of the screw 20 as shown in Figure 2, so that they can be screwed in with a screwdriver. Examples include a screw having a groove 23 cut in the head 21, and a screw 30 consisting of a bolt 31 and a nut 32 shown in FIG.
第４図には、硬組織代替材４０と骨４１とを本発明によ
る骨固定用ねじ４２．４３で固定した状態を示す。ねじ
４２．４３を使用するにあたり、予め、硬組織代替材４
０と骨４１にはねじ溝を切っておく。ねじ頭４２ａは、
外に出しておくようにしても、又は、ねじ頭４３ａのよ
うに頭が出ないようにしてもよい。FIG. 4 shows a hard tissue substitute material 40 and a bone 41 fixed with bone fixing screws 42 and 43 according to the present invention. Before using the screws 42 and 43, prepare the hard tissue substitute material 4 in advance.
Screw grooves are cut in 0 and bone 41. The screw head 42a is
It may be left outside, or the head may not be exposed like the screw head 43a.
以下に実施例により、本発明の人工骨１人工歯及び骨固
定用ねじを更に詳細に説明する。EXAMPLES Below, the artificial bone 1 artificial tooth and bone fixing screw of the present invention will be explained in more detail with reference to Examples.
見１盤上
ヒドロキシアパタイトの粉末及びＰＭＭＡ又はＰＴＦＥ
ＭＡの各モノマーを、ボールミルにて均一に混合し、次
いで加熱重合させて５Ｘ５Ｘ１０■の角柱状の複合体を
製造した。この場合、配合割合は、ヒドロキシアパタイ
トの配合割合を重量比で、３０．４０．５０．７０．８
５及び９５％とした０次いで、製造した角柱状の複合体
を表１に示す組成を有し、温度３７℃に維持した疑似体
液中に３日間浸漬した後、走査型電子顕微鏡で撮影した
写真を画像処理する方法によって表層部に露出している
ヒドロキシアパタイトの面積比を測定した。その結果を
表２に示す。Look at the powder of hydroxyapatite and PMMA or PTFE
The MA monomers were uniformly mixed in a ball mill, and then heated and polymerized to produce a 5 x 5 x 10 square columnar composite. In this case, the blending ratio is 30.40.50.70.8 based on the weight ratio of hydroxyapatite.
5 and 95% 0 Next, the produced prismatic composite had the composition shown in Table 1 and was immersed in a simulated body fluid maintained at a temperature of 37°C for 3 days, and then a photograph was taken with a scanning electron microscope. The area ratio of hydroxyapatite exposed in the surface layer was measured using an image processing method. The results are shown in Table 2.
表２より明らかなように、ヒドロキシアパタイトの配合
割合が５０重量％以上の場合には、ヒドロキシアパタイ
トの面積比も５０％以上となった。As is clear from Table 2, when the blending ratio of hydroxyapatite was 50% by weight or more, the area ratio of hydroxyapatite was also 50% or more.
なお、前記の疑似体液中に７日間浸漬した後には、ヒド
ロキシアパタイトの配合割合が４０重量％の場合にも、
ヒドロキシアパタイトの面積比も５０％以上となった。In addition, after being immersed in the above-mentioned simulated body fluid for 7 days, even when the blending ratio of hydroxyapatite is 40% by weight,
The area ratio of hydroxyapatite was also 50% or more.
しかしながら、重量比が３０％の場合は、１力月浸漬し
た後であっても、ヒドロキシアパタイトの面積比を５０
％以上とすることはできなかった。However, when the weight ratio is 30%, even after one month of immersion, the area ratio of hydroxyapatite is 50%.
% or more was not possible.
表 １ 疑似体液の組成
皇Ａ１」−
参考例１に記載の方法と同様にして角柱状複合体を各々
製造し、更に旋盤にて３閣φ、１０ｍＬの円柱状に加工
した０円柱状に加工した後の、表層部に露出したヒドロ
キシアパタイトの面積比を表３に示す。表３より明らか
なように、加工後であって表面処理以前の状態では、密
度より算出されるよりも、ヒドロキシアパタイト露出量
ははるかに少なかった。これは、旋盤加工の際に、ＰＭ
’ＭＡ又はＰＴＦＥＭＡが一部溶融して、ヒドロキシア
パタイトを薄く被覆したためである。この後。Table 1 Composition of simulated body fluid "A1" - Each prismatic composite was manufactured in the same manner as described in Reference Example 1, and further processed into a cylindrical shape with a diameter of 3 mm and 10 mL using a lathe. Table 3 shows the area ratio of hydroxyapatite exposed in the surface layer after the above treatment. As is clear from Table 3, after processing but before surface treatment, the amount of exposed hydroxyapatite was much smaller than calculated from the density. This is caused by PM during lathe machining.
This is because MA or PTFEMA was partially melted and thinly coated with hydroxyapatite. After this.
プラズマ処理装置（島原製作所製のＬＣＶＤ−２０）に
て、表層部の処理を施したところ１表３に示す如くに顕
著にヒドロキシアパタイトが露出した。更に、実施例１
と同様の方法にて、疑似体液中に３日間浸漬処理したと
ころ、ヒドロキシアパタイト露出面積比は更に増加した
。When the surface layer was treated using a plasma treatment device (LCVD-20 manufactured by Shimabara Seisakusho), hydroxyapatite was significantly exposed as shown in Table 1. Furthermore, Example 1
When the sample was immersed in a simulated body fluid for 3 days in the same manner as above, the hydroxyapatite exposed area ratio further increased.
豊」」」灸
ヒドロキシアパタイト、α−リン酸三カルシウム、β−
リン酸三カルシウム、リン酸四カルシウムの各リン酸カ
ルシウム化合物と、ＰＭＭＡ又はＰＴＦＥＭＡとの各モ
ノマーを各々混合し、参考例１と同様に加熱１重合させ
て４ｍｍφ、８ ｍｕ Ｌの円柱状複合体を作製した。Moxibustion hydroxyapatite, α-tricalcium phosphate, β-
Calcium phosphate compounds such as tricalcium phosphate and tetracalcium phosphate and each monomer of PMMA or PTFEMA were mixed and polymerized by heating in the same manner as in Reference Example 1 to produce a cylindrical composite of 4 mmφ and 8 mu L. did.
次いでプラズマ処理を施した後、参考例１と同様な疑似
体液中に浸漬した。その結果として表層部に露出してい
るヒドロキシアパタイトの面積比が、３０％、４０％。Next, after performing plasma treatment, it was immersed in the same simulated body fluid as in Reference Example 1. As a result, the area ratio of hydroxyapatite exposed in the surface layer was 30% and 40%.
５０％、６０％、７０％及び８０％になるように調節し
、次いで、成人脛骨に作製した欠損４ｍφに、コントロ
ールのヒドロキシアパタイト緻密体と共に充てんし、術
後６力月にて、層殺し、観察した。この結果、いずれの
場合も複合体に直接接して新生骨の生成が認められたが
、特に、ヒドロキシアパタイトを使用した場合に旺盛な
骨の新生がｗＡ察された。又、露出しているリン酸カル
シウム化合物の割合が５０％以上であると、特に新生骨
量が多く認められた。更に、露出ヒドロキシアパタイト
の面積比が７０％以上の場合には、コントロールのヒド
ロキシアパタイト緻密体と比較しても全く同程度の骨の
新生が認められた。又、ＰＭＭＡ及びＰＴＦＥＭＡの相
違による差は認められなかった。Adjusted to 50%, 60%, 70% and 80%, then filled a 4 mφ defect created in an adult tibia with a control hydroxyapatite compact, and 6 months after the surgery, the layer was removed. Observed. As a result, new bone formation was observed in direct contact with the composite in all cases, but particularly vigorous new bone formation was observed when hydroxyapatite was used. Moreover, especially when the proportion of exposed calcium phosphate compound was 50% or more, a large amount of new bone was observed. Furthermore, when the area ratio of exposed hydroxyapatite was 70% or more, new bone formation was observed at exactly the same level as in the control hydroxyapatite compact body. Further, no difference was observed between PMMA and PTFEMA.
次に、骨との接着性を調べるために、リン酸カルシウム
化合物としてヒドロキシアパタイトを使用した複合体に
ついて、打ち抜き試験を実施した。Next, a punching test was conducted on a composite using hydroxyapatite as a calcium phosphate compound in order to examine its adhesion to bone.
その結果を表４に示す。表４の結果より、露出ヒドロキ
シアパタイトの面積比が５０％以上、特に６０％以上の
場合には、コントロールのヒドロキシアパタイト緻密体
と比較して、はぼ同程度の接着力を示した。７０％以上
では、更に接着力が増加した。又、ＰＭＭＡ及びＰＴＦ
ＥＭＡの相違しこ去】１１１
ヒドロキシアパタイト粉末８０重量部、ＰＭＭＡ２０重
量部又はＰＴＦＥＭＡ２０重量部を各々混合し、参考例
１と同様に加熱重合した後、直径１ｍのチタン捧を芯と
して第１図に示すようなねじ１０の全長にねたりねじ山
１２が切っであるねじを成形加工した。次いで該ねじ１
０の表面部をプラズマ処理してから、参考例１と同様な
疑似体液中に３日間浸漬した。The results are shown in Table 4. From the results in Table 4, when the area ratio of exposed hydroxyapatite was 50% or more, especially 60% or more, adhesive strength was almost the same as that of the control hydroxyapatite dense body. At 70% or more, the adhesive strength further increased. Also, PMMA and PTF
Differences in EMA] 111 80 parts by weight of hydroxyapatite powder, 20 parts by weight of PMMA or 20 parts by weight of PTFEMA were mixed, heated and polymerized in the same manner as in Reference Example 1, and then a titanium plate with a diameter of 1 m was used as a core as shown in Fig. 1. A screw with twisted threads 12 cut over the entire length of the screw 10 as shown was formed. Then the screw 1
The surface of the sample 0 was subjected to plasma treatment, and then immersed in the same simulated body fluid as in Reference Example 1 for 3 days.
この結果、表層部に露出しているヒドロキシアパタイト
の面積比はＰＭＭＡを用いた場合８５％。As a result, the area ratio of hydroxyapatite exposed in the surface layer was 85% when PMMA was used.
ＰＴＦＥＭＡを用いた場合８７％となった。When PTFEMA was used, it was 87%.
次に得られたねじ各々を、成犬脛骨に作製したねじ状の
欠損にねじこみ、適役６カ月まで経時的にｌｌＫ察した
。この結果、新生骨の量が多く、特に早期においては比
較例１に比べてはるかに多量の新生骨が生成していた。Next, each of the screws obtained was screwed into a screw-shaped defect created in the tibia of an adult dog, and the IlK was observed over time until 6 months of fit. As a result, the amount of new bone was large, and especially in the early stage, a much larger amount of new bone was generated than in Comparative Example 1.
又、ＰＭＭＡ及びＰＴＦＥＭＡの相違による差は認めら
れなかった。Further, no difference was observed between PMMA and PTFEMA.
ル絞旌よ
ねじの表面部をプラズマ処理しない以外は、実施例１と
同様に人工骨用ネジを製造した。得られたねじは、ねじ
切り時に、ＰＭＭＡ、ＰＴＦＥＭＡが溶融し、ヒドロキ
シアパタイト表層部を被覆したため、露出割合はＰＭＭ
Ａを用いた場合３１％、ＰＴＦＥＭＡを用いた場合３３
％となった。An artificial bone screw was manufactured in the same manner as in Example 1, except that the surface portion of the screw was not subjected to plasma treatment. In the obtained screw, PMMA and PTFEMA melted during thread cutting and covered the hydroxyapatite surface layer, so the exposed ratio was PMM.
31% when using A, 33% when using PTFEMA
%.
これらを実施例１と同様に成犬脛骨に作製したねじ状の
欠損にねじこみ、術後６力月まで経時的にｉ察したとこ
ろ、新生骨の発生が少量であり、実用性に欠けていた。These were screwed into a screw-shaped defect created in the tibia of an adult dog in the same manner as in Example 1, and observed over time until 6 months after the surgery. As a result, a small amount of new bone had been generated, which was not practical. .
本発明による人工骨、人工歯及び骨固定用ねじは、人工
骨等が容易に製造できる範囲内のリン酸カルシウム化合
物及び合成有機重合体の混合割合であるにもかかわらず
、製造した人工骨等の表層部に、リン酸カルシウム化合
物を表面に露出させ生体親和性を向上させることができ
る。又、本発明では、加工により、生体組織と接触する
表層部が一時的に合成有機重合体薄膜にて被覆された場
合であっても、容易に十分な面積比のリン酸カルシウム
化合物を露出させることが可能であり、また製造法にお
いても、容易に且つ特殊な装置を必要としないので工業
的にも非常に有用である。Although the artificial bone, artificial tooth, and bone fixing screw according to the present invention have a mixing ratio of a calcium phosphate compound and a synthetic organic polymer within a range that allows the artificial bone to be easily manufactured, the surface layer of the manufactured artificial bone, etc. Partly, a calcium phosphate compound can be exposed on the surface to improve biocompatibility. Furthermore, in the present invention, even if the surface layer that comes into contact with living tissue is temporarily covered with a synthetic organic polymer thin film due to processing, it is possible to easily expose a sufficient area ratio of the calcium phosphate compound. In addition, the manufacturing method is easy and does not require special equipment, so it is very useful industrially.
第１図は１本発明による骨固定用ねじの一例を示す側面
略図、第２図及び第３図は、各々他の例を示す側面略図
、第４図は、本発明による骨固定用ねじを使用して骨を
固定した状態を示す断面略図である。
１０．２０．３０・・ねじ、１１．２１・・ねじの頭、
１２．２２・・ねじ山、２３・・溝、３１・・ボルト、
３２・・ナツト、４０・・硬組織代替材、４１・・骨、
４２．４３・・固定用ねじ。
４２ａ、４３ａ・・・ねじ山。FIG. 1 is a schematic side view showing one example of a bone fixation screw according to the present invention, FIGS. 2 and 3 are side views schematically showing other examples, and FIG. FIG. 2 is a schematic cross-sectional view showing a state in which bones are fixed using the device. 10.20.30...screw, 11.21...screw head,
12.22...screw thread, 23...groove, 31...bolt,
32... nuts, 40... hard tissue substitute material, 41... bone,
42.43...Fixing screw. 42a, 43a...screw threads.
Claims (1)
有機重合体６０〜５重量％とを含有する人工骨、人工歯
及び骨固定用ねじであって、生体組織と接触する表層部
にリン酸カルシウム化合物を面積比で５０％以上露出さ
せることを特徴とする人工骨、人工歯及び骨固定用ねじ
。 ２）人工骨、人工歯及び骨固定用ねじを製造するにあた
り、リン酸カルシウム化合物及び合成有機重合体の原料
モノマーを混合し、次いで加熱、重合した後に、所望の
形状に加工し、更に表層部に表面処理を施すことにより
リン酸カルシウム化合物を露出させることを特徴とする
人工骨、人工歯及び骨固定用ねじの製造方法。[Scope of Claims] 1) An artificial bone, an artificial tooth, and a bone fixing screw containing 40 to 95% by weight of a calcium phosphate compound and 60 to 5% by weight of a synthetic organic polymer, the surface layer of which comes into contact with living tissue. An artificial bone, an artificial tooth, and a bone fixing screw, characterized in that a calcium phosphate compound is exposed in an area ratio of 50% or more. 2) In manufacturing artificial bones, artificial teeth, and screws for bone fixation, raw material monomers for calcium phosphate compounds and synthetic organic polymers are mixed, then heated and polymerized, processed into the desired shape, and further coated on the surface layer. A method for producing an artificial bone, an artificial tooth, and a screw for bone fixation, the method comprising exposing a calcium phosphate compound through treatment.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1027652A JPH02209148A (en) | 1989-02-08 | 1989-02-08 | Artificial bone, artificial tooth, bone fixing screw and its production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1027652A JPH02209148A (en) | 1989-02-08 | 1989-02-08 | Artificial bone, artificial tooth, bone fixing screw and its production |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02209148A true JPH02209148A (en) | 1990-08-20 |
| JPH0533633B2 JPH0533633B2 (en) | 1993-05-20 |
Family
ID=12226853
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1027652A Granted JPH02209148A (en) | 1989-02-08 | 1989-02-08 | Artificial bone, artificial tooth, bone fixing screw and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02209148A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05131000A (en) * | 1991-05-13 | 1993-05-28 | Eberle Medizintechnische Elemente Gmbh | Transplantation piece |
| JPH05237137A (en) * | 1991-01-10 | 1993-09-17 | Shinsuke Takasugi | Bar hole button for fixing cranial knochenschallappen |
| US8241357B2 (en) | 2007-04-25 | 2012-08-14 | Jmea Corporation | Prosthesis with a selectively applied bone growth promoting agent |
| US8257395B2 (en) | 2007-09-21 | 2012-09-04 | Jmea Corporation | Spinal fixation with selectively applied bone growth promoting agent |
| JP2013513402A (en) * | 2009-12-11 | 2013-04-22 | ニュー・デント・アクチェンゲゼルシャフト | Implant manufacturing method |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6168054A (en) * | 1984-09-10 | 1986-04-08 | 増原 英一 | Artificial bone and tooth |
| JPS61106149A (en) * | 1984-08-31 | 1986-05-24 | ブリストルーマイヤーズ スクイブ カンパニー | Bone tissue coagulation promoting material, bone implant member and production thereof |
| JPS63102762A (en) * | 1986-10-20 | 1988-05-07 | 丸野 重雄 | Living body compatible composite and its production |
| JPS63270049A (en) * | 1987-04-30 | 1988-11-08 | Ngk Spark Plug Co Ltd | Elastic member for living body |
-
1989
- 1989-02-08 JP JP1027652A patent/JPH02209148A/en active Granted
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61106149A (en) * | 1984-08-31 | 1986-05-24 | ブリストルーマイヤーズ スクイブ カンパニー | Bone tissue coagulation promoting material, bone implant member and production thereof |
| JPS6168054A (en) * | 1984-09-10 | 1986-04-08 | 増原 英一 | Artificial bone and tooth |
| JPS63102762A (en) * | 1986-10-20 | 1988-05-07 | 丸野 重雄 | Living body compatible composite and its production |
| JPS63270049A (en) * | 1987-04-30 | 1988-11-08 | Ngk Spark Plug Co Ltd | Elastic member for living body |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05237137A (en) * | 1991-01-10 | 1993-09-17 | Shinsuke Takasugi | Bar hole button for fixing cranial knochenschallappen |
| JPH05131000A (en) * | 1991-05-13 | 1993-05-28 | Eberle Medizintechnische Elemente Gmbh | Transplantation piece |
| US8241357B2 (en) | 2007-04-25 | 2012-08-14 | Jmea Corporation | Prosthesis with a selectively applied bone growth promoting agent |
| US8679166B2 (en) | 2007-04-25 | 2014-03-25 | Jmea Corporation | Prosthesis with a selectively applied bone growth promoting agent |
| US8257395B2 (en) | 2007-09-21 | 2012-09-04 | Jmea Corporation | Spinal fixation with selectively applied bone growth promoting agent |
| US8734487B2 (en) | 2007-09-21 | 2014-05-27 | Jmea Corporation | Spinal fixation with selectively applied bone growth promoting agent |
| JP2013513402A (en) * | 2009-12-11 | 2013-04-22 | ニュー・デント・アクチェンゲゼルシャフト | Implant manufacturing method |
| US9375294B2 (en) | 2009-12-11 | 2016-06-28 | New Dent Ag | Method for producing implants |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0533633B2 (en) | 1993-05-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Go et al. | An osteoconductive PLGA scaffold with bioactive β-TCP and anti-inflammatory Mg (OH) 2 to improve in vivo bone regeneration | |
| US4578384A (en) | Polylactic-polyglycolic acids combined with an acidic phospholipid-lysozyme complex for healing osseous tissue | |
| Jensen et al. | Comparative study of biphasic calcium phosphates with different HA/TCP ratios in mandibular bone defects. A long‐term histomorphometric study in minipigs | |
| US4902649A (en) | Hard tissue substitute composition | |
| CH632158A5 (en) | BONE REPLACEMENT, BONE COMPOSITE OR PROSTHESE ANCHORING MATERIAL. | |
| US8741982B2 (en) | Bioactive bone cement and method for the production thereof | |
| DE2742128A1 (en) | BONE REPLACEMENT MATERIAL AND THEIR USE | |
| FR2848856A1 (en) | Production of a material useful for making bone implants and prostheses by molding a mixture of a binder and calcium and phosphorus compounds comprises cleaning the surface of the molded piece | |
| KR100738476B1 (en) | Membrane for guided bone regerneration and preparation method thereof | |
| Demirel et al. | Effect of strontium-containing compounds on bone grafts | |
| Ebrahimi | Bone grafting substitutes in dentistry: general criteria for proper selection and successful application | |
| JPH02209148A (en) | Artificial bone, artificial tooth, bone fixing screw and its production | |
| Elkholy et al. | In vivo evaluation of β‐CS/n‐HA with different physical properties as a new bone graft material | |
| JP5717074B2 (en) | Bone grafting or bone filling composition comprising a dihydroxybenzoic acid derivative | |
| Babaremu et al. | Behavioral characteristics of magnesium as a biomaterial for surface engineering application | |
| JPS6168054A (en) | Artificial bone and tooth | |
| Zhang et al. | Enhancement of bone to polylactic acid plate bonding by carbonate apatite coating | |
| El-Maghraby et al. | Preparation, structural characterization, and biomedical applications of gypsum-based nanocomposite bone cements | |
| Nadarajan et al. | Fabrication of 3D-printed bone scaffold of natural hydroxyapatite from fish bones in polylactic acid composite | |
| RU2617050C1 (en) | Bioactive composite material for bone defect replacement and method for its manufacture | |
| JPS6269823A (en) | Calcium phosphate based fiber | |
| JPS62268553A (en) | Screw for fixing bone and hard tissue substitute material | |
| JPH01100048A (en) | Production of calcium phosphate-based set material | |
| JPH0236684B2 (en) | ||
| CN1546177A (en) | Coral hydroxyapatite artificial bone with betatype tricalcium phosphate coating and its preparation |