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JP7779473B2 - Titanium alloy - Google Patents
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JP7779473B2 - Titanium alloy - Google Patents

Titanium alloy

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JP7779473B2
JP7779473B2 JP2021143907A JP2021143907A JP7779473B2 JP 7779473 B2 JP7779473 B2 JP 7779473B2 JP 2021143907 A JP2021143907 A JP 2021143907A JP 2021143907 A JP2021143907 A JP 2021143907A JP 7779473 B2 JP7779473 B2 JP 7779473B2
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titanium alloy
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titanium
alloy
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雄京 高田
正敏 高橋
健太 寺井
圭太 伊藤
陽介 山崎
慎太郎 新山
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Tohoku University NUC
Ishifuku Metal Industry Co Ltd
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Ishifuku Metal Industry Co Ltd
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Description

本発明は、チタン合金に関するものである。特に、歯科補綴物や医療機器として用いることを特徴とするチタン合金に関するものである。 The present invention relates to titanium alloys. In particular, it relates to titanium alloys that are suitable for use in dental prostheses and medical devices.

医療現場において、主に生体と直接接触するような用途では、材料が生体へ与える影響を限りなく抑えることが求められており、従来から貴金属やチタン合金などの細胞毒性やアレルギー性の少ない、生体適合性の高い材料が利用されてきた。しかしながら、材料自体の生体への影響もさることながら、生体内で使用される過程において、材料表面で細菌や菌体外多糖により形成されるバイオフィルムが生体に各種疾患を引き起こす原因となることが指摘されており、従来の材料ではバイオフィルムの形成に対する対策が不十分であった。このことから、バイオフィルムに対する付着増殖抑制機能(以下、制菌性とする)を付与したチタン銀合金が提案されている。 In medical settings, applications that primarily involve direct contact with living organisms require that materials have as little impact on the organism as possible. For this reason, highly biocompatible materials with low cytotoxicity and allergenicity, such as precious metals and titanium alloys, have traditionally been used. However, in addition to the effects of the materials themselves on the organism, it has been pointed out that biofilms formed by bacteria and exopolysaccharides on the surface of materials during use within the body can cause various diseases in the organism, and conventional materials have been insufficient in preventing biofilm formation. For this reason, titanium-silver alloys with biofilm adhesion and growth inhibitory properties (hereafter referred to as bacteriostatic properties) have been proposed.

特許文献1には、チタンに銀を添加することで、金属の表面特性を制御し、口腔内の常在菌叢への影響を抑えつつ、生体に有害な影響を及ぼしうるバイオフィルム形成を抑制可能な制菌性を有するチタン銀合金が開示されている。 Patent Document 1 discloses a titanium-silver alloy that, by adding silver to titanium, controls the surface properties of the metal, reducing its impact on the normal bacterial flora in the oral cavity and inhibiting the formation of biofilms that can have harmful effects on the living body.

特開2010-121153Patent Publication No. 2010-121153

しかしながら、特許文献1に記載のチタン銀合金は、歯科技工及び医療機器製造上必要となる、任意の形状に加工可能な加工性を有し、長期的に制菌性が維持されるものの、歯科補綴物や、ガイドワイヤ、ステント、インプラント等の医療機器への適用に際して、機械的特性には改良の余地があった。特に、デンチャーやブリッジの様に、咬合により大きな負荷がかかる大型の歯科補綴物等では、機械的特性が重要視されており、制菌性と加工性、高い機械的特性を併せ持つ材料が求められている。 However, while the titanium-silver alloy described in Patent Document 1 has the workability to be processed into any shape required for dental prostheses and medical device manufacturing, and maintains its antibacterial properties over the long term, there is room for improvement in its mechanical properties when applied to dental prostheses and medical devices such as guide wires, stents, and implants. Mechanical properties are particularly important for large dental prostheses such as dentures and bridges, which are subject to significant loads due to occlusion, and there is a demand for materials that combine antibacterial properties, workability, and high mechanical properties.

そこで本発明の目的は、制菌性と加工性を有しつつ、歯科補綴物や医療機器に適用可能な、高い機械的特性を備えたチタン合金を提供することにある。 The object of the present invention is to provide a titanium alloy that is antibacterial and easy to process, while also possessing high mechanical properties that make it suitable for use in dental prostheses and medical devices.

本発明者らは、鋭意検討を重ねた結果、Ti、Ag、Nb及びCuを最適な組成範囲で配合した合金とすることで、制菌性と加工性を有しつつ、更には、高い機械的特性を具備する、チタン合金を開発するに至った。 After extensive research, the inventors have developed a titanium alloy that combines Ti, Ag, Nb, and Cu in an optimal composition range, resulting in antibacterial properties, workability, and excellent mechanical properties.

すなわち、前述した目的は、Agを3~25mass%、Nbを0.5~30mass%、Cuを0.1~7.5mass%、残部がTi であることを特徴とするチタン合金によって達成される。このチタン合金は、例えば、歯科補綴用の材料として用いることができ、また、医療機器用の材料として用いることができる。 That is, the above-mentioned objectives are achieved by a titanium alloy characterized by 3 to 25 mass% Ag, 0.5 to 30 mass% Nb, 0.1 to 7.5 mass% Cu, and the balance being Ti. This titanium alloy can be used, for example, as a material for dental prosthetics and as a material for medical devices.

本発明に従うと、制菌性と加工性を有しつつ、歯科補綴物や、ガイドワイヤ、ステント、インプラント等の医療機器として必要な、高い機械的強度を併せ持つチタン合金を提供することができる。 The present invention makes it possible to provide a titanium alloy that has antibacterial properties and workability, while also possessing the high mechanical strength required for dental prostheses and medical devices such as guidewires, stents, and implants.

以下、本発明の実施形態について具体的に説明する。 The following describes in detail an embodiment of the present invention.

本発明は、Agを3~25mass%、Nbを0.5~30mass%、Cuを0.1~7.5mass%、残部がTiであることを特徴とするチタン合金である。 The present invention is a titanium alloy characterized by 3 to 25 mass% Ag, 0.5 to 30 mass% Nb, 0.1 to 7.5 mass% Cu, and the balance being Ti.

Agは、合金に添加することで制菌性を発現する。その添加量は、3mass%未満では制菌性が劣り、一方で25mass%を超えると伸びが不十分になる。好ましくは4~23mass%である。 Adding Ag to alloys imparts antibacterial properties. If the amount added is less than 3 mass%, antibacterial properties are poor, while if it exceeds 25 mass%, elongation becomes insufficient. The preferred amount is 4 to 23 mass%.

NbとCuを同時にTiAg合金に添加することで、制菌性を維持したまま、硬さと耐力を向上させることが可能となる。Nbのみの単独添加では硬さや耐力の向上は見込めず、Cuのみを硬さや耐力の向上に必要なだけ添加すると、加工性が著しく低下してしまう。 By adding Nb and Cu simultaneously to a TiAg alloy, it is possible to improve hardness and yield strength while maintaining antibacterial properties. Adding Nb alone does not improve hardness or yield strength, and adding only Cu in the amount necessary to improve hardness and yield strength significantly reduces workability.

NbとCuを同時に添加するに際し、Nbの添加量は0.5mass%未満では十分な加工性が得られなくなり、30mass%を超えると耐力が不十分になる。Nbの添加量は、好ましくは0.7~27mass%、さらに好ましくは3~17mass%である。
一方Cuの添加量は0.1mass%未満では十分な硬さと耐力が得られなくなり、7.5mass%を超えると加工性が不十分になる。好ましくは0.3~6mass%である。
When Nb and Cu are added simultaneously, if the amount of Nb added is less than 0.5 mass%, sufficient workability cannot be obtained, and if it exceeds 30 mass%, the yield strength becomes insufficient. The amount of Nb added is preferably 0.7 to 27 mass%, more preferably 3 to 17 mass%.
On the other hand, if the amount of Cu added is less than 0.1 mass%, sufficient hardness and yield strength cannot be obtained, and if it exceeds 7.5 mass%, workability becomes insufficient. The preferred amount is 0.3 to 6 mass%.

本発明を以下の実施例にて説明するが、本実施の形態で製造方法が限定されるものではない。 The present invention will be explained in the following examples, but the manufacturing method is not limited to these embodiments.

実施例及び比較例の合金の組成を表1に示す。Ti、Ag、Nb、Cu の原材料を秤量し、表1の組成となるように配合した後、アルゴン雰囲気中でアーク溶解法にて溶解し、各合金インゴットを作製した。 The alloy compositions of the examples and comparative examples are shown in Table 1. The raw materials Ti, Ag, Nb, and Cu were weighed and mixed to obtain the compositions shown in Table 1. They were then melted in an argon atmosphere using an arc melting method to produce alloy ingots.

作製したインゴットに対して、熱間鍛造、次いで熱間圧延した後、熱処理を行うことで、厚さ2mmの板材(実施例1~10、比較例1~3)を作製した。 The produced ingots were hot forged, then hot rolled, and then heat treated to produce 2 mm thick plates (Examples 1-10, Comparative Examples 1-3).

作製した各合金の板材に関して、下記の評価を行った。その結果を表2に示す。 The following evaluations were carried out on the sheets of each alloy produced. The results are shown in Table 2.

加工性は、インゴットから厚さ2mmの板材までの加工にて評価した。厚さ2mmの板材が得られた合金は〇、加工途中で割れが発生して厚さ2mmの板材が得られなかった合金は×として表2に示す。なお、加工性が×の合金に関しては、試験片が作製できず、制菌性と各機械的特性の評価の欄は「―」で示した。 Workability was evaluated by processing the ingot into 2mm thick plates. Alloys from which 2mm thick plates could be obtained are marked with a 〇, and alloys from which cracks occurred during processing and 2mm thick plates could not be obtained are marked with an × in Table 2. Note that for alloys with an × in workability, test specimens could not be prepared, and the columns for the evaluation of antibacterial properties and each mechanical property are marked with a "-".

制菌性は、以下のようなバイオフィルム付着試験で評価した。先ず、試験材を切り出して厚さ2mm、長さ15mm、幅10mmの試験片を作製した。スクロース含有複合液体培地の入った容器に、滅菌処理した試験片を浸漬し、口腔内でのバイオフィルムの形成を模擬する細菌として、Streptococcus mutans を加えて所定の時間嫌気培養した。この試験片を水の入った容器に移し替えて、洗浄した後、ヘラを用いて付着したバイオフィルムを採取して一定量の水に懸濁させて、その濁度からバイオフィルム量を求めた。なお、このバイオフィルム量が少ないほど、その材料の制菌性が優れていることを意味する。制菌性の評価は、純Ti材と比較して、合金のバイオフィルム量の減少率が10%以上であれば〇、合金のバイオフィルム量の減少率が10%未満(バイオフィルム量の増大を含む)であれば×として表2に示す。 Bacteriostatic properties were evaluated using the following biofilm adhesion test. First, test pieces measuring 2 mm thick, 15 mm long, and 10 mm wide were cut from the test material. The sterilized test pieces were immersed in a container containing a sucrose-containing complex liquid medium, and Streptococcus mutans, a bacterium simulating oral biofilm formation, was added and anaerobically cultured for a specified period of time. The test pieces were then transferred to a container containing water and washed. After that, the attached biofilm was collected with a spatula and suspended in a specified amount of water. The biofilm volume was calculated from the turbidity. The smaller the biofilm volume, the better the bacteriostatic properties of the material. Bacteriostatic properties were evaluated as follows: if the reduction in biofilm volume of the alloy compared to pure Ti material was 10% or more, it was marked "Good"; if the reduction in biofilm volume of the alloy was less than 10% (including an increase in biofilm volume), it was marked "X." These are shown in Table 2.

硬さは、試験材から切り出した厚さ2mm、長さ15mm、幅10mmの試験片を用い、マイクロビッカース硬さ試験機で、荷重200gf、保持時間10秒の条件で測定した。その結果を表2に示す。硬さが300HV以上であれば◎、300HV未満かつ270HV以上であれば〇、270HV未満であれば×として評価し、表2に示す。 Hardness was measured using a micro-Vickers hardness tester using test pieces 2 mm thick, 15 mm long, and 10 mm wide cut from the test material, with a load of 200 gf and a holding time of 10 seconds. The results are shown in Table 2. Hardness was evaluated as ◎ if it was 300 HV or higher, 〇 if it was less than 300 HV and 270 HV or higher, and × if it was less than 270 HV, and are shown in Table 2.

耐力は、 試験材から切り出した厚さ2mm、長さ50mm、幅3mmの試験片を用いて、室温、大気中、クロスヘッドスピード1.5mm/minの条件で測定した。比較例1を100%として、比較例1の耐力に対する実施例及び他の比較例の相対的な耐力を表2に示す。また、上記の耐力の比が120%以上であれば◎、120%未満かつ110%以上であれば〇、110%未満であれば×として評価し、表2に示す。 Yield strength was measured at room temperature in air at a crosshead speed of 1.5 mm/min using test pieces 2 mm thick, 50 mm long, and 3 mm wide cut from the test material. Comparative Example 1 is set to 100%, and the relative yield strengths of the Examples and other Comparative Examples relative to that of Comparative Example 1 are shown in Table 2. Furthermore, the yield strength ratio was evaluated as ◎ if it was 120% or greater, 〇 if it was less than 120% and 110% or greater, and × if it was less than 110%, and these results are shown in Table 2.

伸びは、上記の引張試験後の試験片の突き合わせ伸びから求めた。伸びは、JIS T 6123(固定性歯科修復物用非貴金属材料)のタイプ5(高剛性及び高強度が要求される装置)に要求される特性を参考にして、伸びが2%以上であれば〇、伸びが2%未満であれば×として評価し、表2に示す。 Elongation was determined from the butt joint elongation of the test specimen after the above tensile test. Elongation was evaluated based on the properties required for Type 5 (devices requiring high rigidity and high strength) of JIS T 6123 (non-precious metal materials for fixed dental restorations), with an elongation of 2% or more being evaluated as "Good" and an elongation of less than 2% being evaluated as "Poor." The results are shown in Table 2.

以上の結果から、本発明により作製した合金は、制菌性と加工性を有しつつ、歯科補綴物や医療機器として必要な機械的特性を併せ持つことが分かる。従って、本発明によって、医療現場での活用に好適なチタン合金を提供することが可能となる。 These results demonstrate that the alloys produced according to the present invention possess antibacterial properties and workability, while also possessing the mechanical properties required for dental prostheses and medical devices. Therefore, the present invention makes it possible to provide titanium alloys that are suitable for use in medical settings.

Claims (3)

Agを3~25mass%、Nbを0.5~30mass%、Cuを0.1~7.5mass%、残部がTi であり、硬さが270HV以上であり、伸びが2%以上であり、制菌性を有することを特徴とするチタン合金。 A titanium alloy characterized by containing 3-25 mass% Ag, 0.5-30 mass% Nb, 0.1-7.5 mass% Cu, and the balance Ti, having a hardness of 270 HV or more, an elongation of 2% or more, and having antibacterial properties . 歯科補綴用であることを特徴とする請求項1に記載のチタン合金。 The titanium alloy described in claim 1, characterized in that it is used for dental prostheses. 医療機器用であることを特徴とする請求項1に記載のチタン合金。 The titanium alloy described in claim 1, characterized in that it is used for medical devices.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004183017A (en) 2002-11-29 2004-07-02 Ota Kk Surface treatment method for metal titanium based base material and metal titanium based medical material
JP2006515387A (en) 2002-12-18 2006-05-25 アイオニック フュージョン コーポレイション Ionic plasma deposition of anti-microbial surfaces and anti-microbial surfaces obtained therefrom
US20170107627A1 (en) 2014-03-25 2017-04-20 Kyungpook National University Industry-Academic Cooperation Foundation Method for preparing titanium-containing implant by using environmentally-friendly etching composition
CN109022853A (en) 2018-07-18 2018-12-18 昆明理工大学 A kind of preparation method of antibacterial Ti-Nb-Zr-Ag alloy pig

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB8408975D0 (en) * 1984-04-06 1984-05-16 Wood J V Titanium alloys

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004183017A (en) 2002-11-29 2004-07-02 Ota Kk Surface treatment method for metal titanium based base material and metal titanium based medical material
JP2006515387A (en) 2002-12-18 2006-05-25 アイオニック フュージョン コーポレイション Ionic plasma deposition of anti-microbial surfaces and anti-microbial surfaces obtained therefrom
US20170107627A1 (en) 2014-03-25 2017-04-20 Kyungpook National University Industry-Academic Cooperation Foundation Method for preparing titanium-containing implant by using environmentally-friendly etching composition
CN109022853A (en) 2018-07-18 2018-12-18 昆明理工大学 A kind of preparation method of antibacterial Ti-Nb-Zr-Ag alloy pig

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