JP5656138B1 - Phosphor bronze alloy having antibacterial properties and article using the same - Google Patents
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Abstract
【課題】 リン青銅の抗菌性を検証し、人体との接触による変色を軽減する方法を提供して、リン青銅の抗菌性を活用し得る用途を提案する。【解決手段】 リン青銅合金の組成を、11重量%以下(0を含まない)のスズと、0.35重量%以下(0を含まない)のリンとを含み、残部が銅とすることにより、優れた抗菌性を発現する。変色の防止には、粒度が40〜200の砥粒を用いてグラインダ加工やショットブラスト加工により、表面を粗面化することで対処できる。この抗菌性を有するリン青銅で、医療機関などの手摺、ドアノブ、その他の手で直接触れる部分を覆うことで、感染症の蔓延などを未然に防止できる。【選択図】なしPROBLEM TO BE SOLVED: To provide a method for verifying the antibacterial property of phosphor bronze, providing a method for reducing discoloration due to contact with a human body, and utilizing the antibacterial property of phosphor bronze. SOLUTION: The composition of a phosphor bronze alloy includes 11 wt% or less (excluding 0) tin and 0.35 wt% or less (not including 0) phosphorus, with the balance being copper. Expresses excellent antibacterial properties. Prevention of discoloration can be dealt with by roughening the surface by grinder processing or shot blast processing using abrasive grains having a particle size of 40-200. By covering phosphoric bronze with antibacterial properties, such as handrails of medical institutions, door knobs, and other parts that are directly touched by hands, it is possible to prevent the spread of infectious diseases. [Selection figure] None
Description
本発明は、抗菌性を有するリン青銅合金と、それを用いて抗菌性を付与した、物品に関するものである。 The present invention relates to a phosphor bronze alloy having antibacterial properties and an article provided with the antibacterial properties.
銅、銀、スズなどが殺菌性や抗菌性を有することは、従来から知られていて、様々な分野に使用されている。これらの金属が殺菌性や抗菌を発現する理由としては、水に溶けて生じるイオンが、微生物の細胞壁や細胞膜を破壊したり、酵素やタンパク質と結合して、活性や代謝機能を低下させたりすることによると言われている。また、イオン化する際に放出される電子が、空気中や水中に溶存する酸素の一部を活性化し、微生物中の有機物を化学的に攻撃することも、殺菌性や抗菌性の要因になると言われている。 It has been conventionally known that copper, silver, tin and the like have bactericidal and antibacterial properties and are used in various fields. The reason why these metals exhibit bactericidal and antibacterial properties is that ions generated by dissolving in water destroy the cell walls and cell membranes of microorganisms, or bind to enzymes and proteins to reduce activity and metabolic functions. It is said that it depends. In addition, it is said that the electrons released during ionization activate part of the oxygen dissolved in the air and water and chemically attack the organic matter in the microorganism, which is also a factor of bactericidal and antibacterial properties. It has been broken.
一方で、リン青銅はスズを含む合金で、機械的な強度や導電性に優れ、加工性にも優れていることから、電子部品や各種電機製品に用いられている。加工性に優れていることから、用途に合わせた形状に加工することが容易で、この特徴と、殺菌性あるいは抗菌性の両方を活用することにより、従来とは異なる用途展開が期待できる。 On the other hand, phosphor bronze is an alloy containing tin, is excellent in mechanical strength and conductivity, and is excellent in workability. Therefore, phosphor bronze is used in electronic parts and various electric products. Since it is excellent in processability, it can be easily processed into a shape suitable for the application. By utilizing both this characteristic and bactericidal or antibacterial properties, application development different from the conventional one can be expected.
このような観点から、殺菌性や抗菌性を必要とする分野への銅合金の使用例を概観すると、例えば、銅線を編み込むことにより、水虫の予防効果を付与した靴下が挙げられる。また、特許文献1には、銅や銀などの金属で構成した金網を用いた、水系洗浄液を濾過する濾過装置が開示されている。 From such a point of view, an overview of examples of the use of copper alloys in fields that require bactericidal and antibacterial properties includes socks that have been given the effect of preventing athlete's foot by knitting copper wire. Further, Patent Document 1 discloses a filtration device that filters an aqueous cleaning solution using a wire mesh made of a metal such as copper or silver.
また、特許文献2には、銀、銅、亜鉛、スズなどから選ばれる消臭抗菌成分を担持させた酸化チタン粒子と、アミン系化合物からなる抗菌消臭剤が開示されている。しかし、これらはいずれも、人の手などが直接触れるものではなく、例えば、医療機関の通路に付設される手摺などのように、手で直接触れることが使用目的で、しかも高度の殺菌性あるいは抗菌性が要求されるものは、見出せないのが実情である。 Patent Document 2 discloses an antibacterial deodorant comprising titanium oxide particles carrying a deodorant antibacterial component selected from silver, copper, zinc, tin and the like, and an amine compound. However, none of these are directly touched by human hands. For example, they are intended to be touched directly by hand, such as a handrail attached to a passage of a medical institution, and have high sterilization properties or The fact that antibacterial properties are required cannot be found.
この理由としては、リン青銅が、純銅よりも高い抗菌性を示すことが明確に示されていなかったことと、銅及び銅合金は人体との接触により、変色が生じやすいことが挙げられる。 The reason for this is that phosphor bronze was not clearly shown to exhibit higher antibacterial properties than pure copper, and that copper and copper alloys tend to discolor due to contact with the human body.
従って、本発明の課題は、リン青銅の抗菌性を検証し、人体との接触による変色を軽減する方法を提供して、リン青銅の抗菌性を活用し得る用途を提案することにある。 Therefore, the subject of this invention is verifying the antibacterial property of phosphor bronze, providing the method of reducing discoloration by contact with a human body, and proposing the use which can utilize the antibacterial property of phosphor bronze.
本発明は、前記課題に鑑み、リン青銅のスズとリンの含有量と抗菌性との関係を明確化するとともに、表面の性状と変色の顕在化との関係を検討した結果なされたものである。 In view of the above problems, the present invention has been made as a result of clarifying the relationship between the antibacterial property and the content of tin and phosphorus in phosphor bronze and examining the relationship between surface properties and the manifestation of discoloration. .
即ち、本発明は、11重量%以下(0を含まない)のスズと、0.35重量%以下(0を含まない)のリンとを含み、残部が銅と不可避の不純物からなることを特徴とする、抗菌性を有するリン青銅合金である。 That is, the present invention is characterized by containing 11% by weight or less (not including 0) tin and 0.35% by weight or less (not including 0) phosphorus, with the balance being copper and inevitable impurities. And a phosphor bronze alloy having antibacterial properties.
また、本発明は、圧延加工が施され、表面に機械的な粗面化処理を施されてなることを特徴とする、前記の抗菌性を有するリン青銅合金である。 Further, the present invention is the phosphor bronze alloy having antibacterial properties described above, characterized in that the surface is subjected to a rolling process and subjected to a mechanical roughening treatment.
また、本発明は、前記粗面化処理の加工方法が、粒度が40〜200の砥粒を用いたグラインダ加工、粒度が40〜200の砥粒を用いたショットブラスト加工、ヘアライン加工から選ばれる少なくとも1種を含むことを特徴とする、前記の抗菌性を有するリン青銅合金である。 In the present invention, the roughening treatment method is selected from grinder processing using abrasive grains having a particle size of 40 to 200, shot blast processing using abrasive grains having a particle size of 40 to 200, and hairline processing. The phosphor bronze alloy having antibacterial properties described above, characterized by containing at least one kind.
また、本発明は、前記のリン青銅合金の薄板で、表面を被覆してなることを特徴とする物品である。 In addition, the present invention is an article characterized in that the surface is covered with the phosphor bronze alloy thin plate.
本発明者らは、リン青銅合金における、スズとリンの含有量と抗菌性の関係を、微生物の培養試験により検討した結果、スズの含有量が11重量%以下、リンの含有量が0.35重量%以下の領域で、リン青銅合金が顕著な抗菌性を発現することを見出し、本発明をなした。 As a result of examining the relationship between tin and phosphorus contents and antibacterial properties in a phosphor bronze alloy by a culture test of microorganisms, the present inventors have found that the tin content is 11% by weight or less and the phosphorus content is 0.1%. It has been found that phosphor bronze alloys exhibit remarkable antibacterial properties in the region of 35% by weight or less, and have made the present invention.
一般に銅などの抗菌性の要因の一つとして、金属がイオン化する際に放出される電子が、空気中や水中に溶存する酸素の一部を活性化することが考えられているのは、前記の通りである。リン青銅合金においては、合金を構成する成分の、イオン化ポテンシャルの相異とそれに付随するイオン化傾向の相異により、各成分の間で電子の授受が生じることが、特定の組成範囲における、このような結果に繋がったものと解される。 In general, as one of the antibacterial factors such as copper, it is considered that electrons released when a metal is ionized activates part of oxygen dissolved in the air or water. It is as follows. In a phosphor bronze alloy, the transfer of electrons between components due to the difference in ionization potential and the accompanying ionization tendency of the components constituting the alloy can occur in a specific composition range. It is understood that it was connected to the result.
また、一般に金属表面の外観は、鏡面のように研磨した状態と、粗面化した状態とでは、大きく異なり、特に適当な表面粗さに粗面化すると、例えば人の手の皮脂のような異物の付着や、酸化による変色が目立たなくなる。本発明者は、この現象に着目し、粗面化の条件の検討により、表面の変色を解消した。 In general, the appearance of a metal surface is greatly different between a polished state like a mirror surface and a roughened state, and particularly when roughened to an appropriate surface roughness, for example, sebum in human hands. Adherence of foreign matter and discoloration due to oxidation become inconspicuous. The inventor paid attention to this phenomenon and solved the discoloration of the surface by examining the conditions of roughening.
次に、リン青銅合金のスズとリンの含有量と抗菌性の検討の説明により、本発明の実施の形態について説明する。 Next, an embodiment of the present invention will be described by explaining the contents of tin and phosphorus in the phosphor bronze alloy and studying antibacterial properties.
まず、電気銅、スズ、リンを溶解、鋳造し、60mm×60mm×200mmの角柱状のインゴットを得た。ターゲット組成は、スズが、0、1.0、2.0、2.5、3.0、5.0、5.5、6.7重量%、リンが0.09重量%、残部が銅である。 First, electrolytic copper, tin, and phosphorus were melted and cast to obtain a prismatic ingot of 60 mm × 60 mm × 200 mm. The target composition is 0, 1.0, 2.0, 2.5, 3.0, 5.0, 5.5, 6.7% by weight for tin, 0.09% by weight for phosphorus, and the balance for copper. It is.
このインゴットから、寸法が10mm×28mm×28mmの、抗菌性試験用試料を切り出し、JIS L 1902に準じたハロー試験を行った。試験に用いた菌は、黄色ブドウ球菌、大腸菌、緑膿菌の3種類である。図1は、ハロー試験の一例を示す写真で、ここに示したのは、黄色ブドウ球菌の例である。 A sample for antibacterial test having dimensions of 10 mm × 28 mm × 28 mm was cut out from the ingot, and a halo test in accordance with JIS L 1902 was performed. There are three types of bacteria used in the test: Staphylococcus aureus, Escherichia coli, and Pseudomonas aeruginosa. FIG. 1 is a photograph showing an example of a halo test, which shows an example of Staphylococcus aureus.
ハロー試験では、シャーレの中に菌を培養し、中央に試験片を置いて一定時間保持する。そして試験片周辺の菌が消滅した、ハローと称される領域の幅を測定する。試験は3菌種に対し3回異なる試験片を用いて行った。ハロー幅は、図1にA、B、C、Dで示したように、試験片の4辺に対して測定するので、1条件に対し12回の測定を行った In the halo test, bacteria are cultured in a petri dish, and a test piece is placed in the center and held for a certain period of time. And the width | variety of the area | region called the halo where the microbe around the test piece disappeared is measured. The test was performed using three different test pieces for the three bacterial species. As shown by A, B, C, and D in FIG. 1, the halo width is measured for four sides of the test piece.
表1は、試験に用いたリン青銅合金のスズ含有量毎に、ハロー幅の12回の測定値の平均値をまとめた表である。また、図2は表1に示したハロー試験の結果を、横軸をスズ含有量、縦軸をハロー幅として示した図である。 Table 1 is a table summarizing the average values of 12 measurements of the halo width for each tin content of the phosphor bronze alloy used in the test. FIG. 2 is a graph showing the results of the halo test shown in Table 1, with the horizontal axis representing the tin content and the vertical axis representing the halo width.
表1と図2に示したように、本試験条件の範囲では、一定以上の抗菌性が認められる。つまり、スズを添加することで、いずれの菌においても、純銅よりも抗菌効果の向上が認められることが明らかである。また,菌種によって、スズ添加の効果が異なる可能性があることがわかった。黄色ブドウ球菌と大腸菌ではスズ含有量が1重量%のときにハロー幅のピークが見られ、それ以上の領域の含有量では減少するが、スズ含有量3重量%程度から再び増加し、安定となる。緑膿菌のスズ含有量1重量%でのハロー幅は、他の二つの菌よりも小さいが、スズ含有量の増加に伴い、他の二つの菌と同じような挙動を示した。 As shown in Table 1 and FIG. 2, antibacterial properties exceeding a certain level are recognized within the range of this test condition. That is, by adding tin, it is apparent that the antibacterial effect is improved over pure copper in any bacteria. It was also found that the effect of tin addition may differ depending on the bacterial species. In S. aureus and Escherichia coli, a halo width peak is observed when the tin content is 1% by weight, and it decreases when the tin content is higher than that. Become. Although the halo width of the Pseudomonas aeruginosa at a tin content of 1% by weight was smaller than the other two bacteria, it showed the same behavior as the other two bacteria as the tin content increased.
図3は、本発明に係る青銅合金表面を、グラインダを用いて粗面化した例の写真である。ここで粗面化加工に用いたグラインダの、砥石の粒度は120である。通常の圧延仕上がり面では、直接手で触れると指紋跡が目立つが、表面をこのように機械加工で粗面化することにより、指紋跡の視認が困難になった。なお、粗面化の方法としてはグラインダの他に、ショットブラスト加工、ヘアライン加工などが挙げられ、同様の効果が得られることは勿論である。 FIG. 3 is a photograph of an example of roughening the surface of the bronze alloy according to the present invention using a grinder. Here, the grindstone used in the roughening process has a grindstone particle size of 120. On the normal finished surface, fingerprint marks are conspicuous when directly touched with a hand. However, since the surface is roughened by machining as described above, it is difficult to visually recognize the fingerprint marks. In addition to the grinder, the surface roughening method includes shot blasting, hairline processing, and the like, and it goes without saying that the same effect can be obtained.
図4は、約0.2mmの厚さに圧延し、表面を粗面化した、本発明のリン青銅合金薄板を、手摺表面に取り付けた一例を示す斜視図である。図4において、1は手摺、2はリン青銅合金薄板、3a及び3bは手摺1を壁面に取り付けるためのフランジ部である。医療機関や高齢者の介護施設の通路や出入り口には、ここに示したように、手摺やドアノブなどの直接手で触れる部分を、本発明のリン青銅合金の薄板で覆うことにより、感染症の蔓延を事前に防止することができる。 FIG. 4 is a perspective view showing an example in which the phosphor bronze alloy thin plate of the present invention, which has been rolled to a thickness of about 0.2 mm and roughened, is attached to the handrail surface. In FIG. 4, 1 is a handrail, 2 is a phosphor bronze alloy thin plate, 3a and 3b are flange portions for attaching the handrail 1 to a wall surface. Covering the passages and entrances of medical institutions and elderly care facilities, as shown here, with hand-touched parts such as handrails and doorknobs with the thin sheet of phosphor bronze alloy of the present invention, Invasion can be prevented in advance.
以上に示したように、本発明によれば、抗菌性に優れたリン青銅合金を提供することができる。なお、本発明は、前記実施の形態に限定されるものではなく、本発明の分野における通常の知識を有する者であれば想到し得る、各種変形、修正を含む、本発明の要旨を逸脱しない範囲の設計変更があっても、本発明に含まれることは勿論である。 As described above, according to the present invention, a phosphor bronze alloy having excellent antibacterial properties can be provided. The present invention is not limited to the above-described embodiment, and does not depart from the gist of the present invention, including various modifications and corrections that can be conceived by those having ordinary knowledge in the field of the present invention. Of course, even if there is a design change in the range, it is included in the present invention.
1・・・手摺
2・・・リン青銅合金薄板
3a,3b・・・フランジ部DESCRIPTION OF SYMBOLS 1 ... Handrail 2 ... Phosphor bronze alloy thin plate 3a, 3b ... Flange part
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JP2021123786A (en) * | 2020-02-07 | 2021-08-30 | 株式会社原田伸銅所 | Phosphor bronze alloy whose antibacterial property is amplified by roughening surface using anodic oxidation method in which the surface is subjected to immersion treatment for a fixed time |
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KR20220158096A (en) | 2021-05-21 | 2022-11-29 | 하라다 메탈 인더스트리 컴퍼니 리미티드 | Phosphor bronze alloy and articles using the same |
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