JP2020186419A - Manufacturing method of sterilization member, and sterilization member - Google Patents
Manufacturing method of sterilization member, and sterilization member Download PDFInfo
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- 230000001954 sterilising effect Effects 0.000 title claims abstract description 39
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 25
- 238000004659 sterilization and disinfection Methods 0.000 title description 4
- 238000005245 sintering Methods 0.000 claims abstract description 43
- 239000000843 powder Substances 0.000 claims abstract description 33
- 239000010419 fine particle Substances 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 22
- 239000000463 material Substances 0.000 claims abstract description 16
- 238000001704 evaporation Methods 0.000 claims abstract description 8
- 229910052709 silver Inorganic materials 0.000 claims description 14
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 12
- 239000004332 silver Substances 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 8
- 238000010891 electric arc Methods 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 238000000465 moulding Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 19
- 239000002994 raw material Substances 0.000 abstract description 5
- 238000010586 diagram Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 10
- 241000894006 Bacteria Species 0.000 description 9
- 125000001475 halogen functional group Chemical group 0.000 description 8
- 238000002490 spark plasma sintering Methods 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 7
- 239000007789 gas Substances 0.000 description 6
- 230000001580 bacterial effect Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 230000007423 decrease Effects 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 3
- 229910052721 tungsten Inorganic materials 0.000 description 3
- 239000010937 tungsten Substances 0.000 description 3
- 241000588724 Escherichia coli Species 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 239000000498 cooling water Substances 0.000 description 2
- 238000012258 culturing Methods 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 239000011858 nanopowder Substances 0.000 description 2
- IIZPXYDJLKNOIY-JXPKJXOSSA-N 1-palmitoyl-2-arachidonoyl-sn-glycero-3-phosphocholine Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@H](COP([O-])(=O)OCC[N+](C)(C)C)OC(=O)CCC\C=C/C\C=C/C\C=C/C\C=C/CCCCC IIZPXYDJLKNOIY-JXPKJXOSSA-N 0.000 description 1
- 229920001817 Agar Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 235000010469 Glycine max Nutrition 0.000 description 1
- 244000068988 Glycine max Species 0.000 description 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
- 239000008272 agar Substances 0.000 description 1
- 230000000843 anti-fungal effect Effects 0.000 description 1
- 229940121375 antifungal agent Drugs 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000005018 casein Substances 0.000 description 1
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 1
- 235000021240 caseins Nutrition 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000009036 growth inhibition Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000787 lecithin Substances 0.000 description 1
- 235000010445 lecithin Nutrition 0.000 description 1
- 229940067606 lecithin Drugs 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002504 physiological saline solution Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 239000000244 polyoxyethylene sorbitan monooleate Substances 0.000 description 1
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 description 1
- 229920000053 polysorbate 80 Polymers 0.000 description 1
- 229940068968 polysorbate 80 Drugs 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
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Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/25—Process efficiency
Landscapes
- Apparatus For Disinfection Or Sterilisation (AREA)
- Disinfection, Sterilisation Or Deodorisation Of Air (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
- Powder Metallurgy (AREA)
Abstract
【課題】Ａｇを主材料とし、高い殺菌効果を有し、かつ製造が容易な殺菌部材、及びその製造方法を提供する。【解決手段】原材料として用いられるＡｇ粉末をアークプラズマ強制蒸発法によって製造する粉末生成工程と、Ａｇ粉末が高圧で一軸加圧された状態で、パルス電流が流されることによる放電によって加熱されて焼結される焼結工程とを具備する、殺菌部材の製造方法。この焼結体を、元のＡｇ微粒子の形態を反映した多孔質とすることができ、これによってＡｇの実効的な表面積を大きくすることができ、殺菌効果を高くできる。【選択図】図１PROBLEM TO BE SOLVED: To provide a sterilizing member using Ag as a main material, having a high sterilizing effect and being easy to manufacture, and a method for producing the same. SOLUTION: This is a powder generation step of producing Ag powder used as a raw material by an arc plasma forced evaporation method, and in a state where Ag powder is uniaxially pressurized at high pressure, it is heated and fired by electric discharge due to a pulse current flowing through it. A method for manufacturing a sterilizing member, comprising a sintering step to be tied. The sintered body can be made porous reflecting the morphology of the original Ag fine particles, whereby the effective surface area of Ag can be increased and the bactericidal effect can be enhanced. [Selection diagram] Fig. 1
Description
本発明は、殺菌効果を有する殺菌部材の製造方法、殺菌部材に関する。 The present invention relates to a method for producing a sterilizing member having a bactericidal effect and a sterilizing member.
非特許文献１、２に記載されるように、ある種の金属（金属イオン）には殺菌効果があり、その中でも特に銀（Ａｇ）は高い効果を奏することが知られている。特許文献１には、このためにＡｇを構成要素として用いた殺菌装置が記載されている。このような殺菌装置においては、露出したＡｇ表面によって殺菌が行われる。 As described in Non-Patent Documents 1 and 2, it is known that certain metals (metal ions) have a bactericidal effect, and among them, silver (Ag) has a particularly high effect. Patent Document 1 describes a sterilizer using Ag as a component for this purpose. In such a sterilizer, sterilization is performed by the exposed Ag surface.
Ａｇを用いた従来の殺菌装置においては、Ａｇで構成され殺菌効果を有する部分と、殺菌装置を構成するために上記のＡｇで構成された部分と組み合わせられる他の材料で構成された部分とで構成される。このため、このような殺菌装置の殺菌効果はその全体の大きさに対して十分ではない、あるいは、殺菌装置を大型とした場合には、その製造が容易ではないために特に高価となる、等の問題があった。 In a conventional sterilizer using Ag, a portion composed of Ag and having a sterilizing effect and a portion composed of another material combined with the above-mentioned portion composed of Ag to form the sterilizer It is composed. For this reason, the sterilizing effect of such a sterilizing device is not sufficient for its overall size, or when the sterilizing device is made large, it is particularly expensive because it is not easy to manufacture. There was a problem.
このため、Ａｇを主材料とし、高い殺菌効果を有し、かつ製造が容易な殺菌部材が望まれた。 Therefore, a sterilizing member using Ag as a main material, having a high sterilizing effect, and being easy to manufacture has been desired.
本発明は、かかる問題点に鑑みてなされたものであり、上記問題点を解決する発明を提供することを目的とする。 The present invention has been made in view of such problems, and an object of the present invention is to provide an invention for solving the above problems.
本発明は、上記課題を解決すべく、以下に掲げる構成とした。
本発明の殺菌部材の製造方法は、銀（Ａｇ）を主成分として構成された殺菌部材の製造方法であって、水素を含有する減圧雰囲気中においてＡｇで構成された銀母材に対してアーク放電を生じさせてＡｇを気化させてから微粒子として固化させるアークプラズマ強制蒸発法によって平均粒径が１４ｎｍ〜１４４ｎｍの範囲であるＡｇ微粒子を生成する粉末生成工程と、前記Ａｇ微粒子で構成された粉末を加圧、成形した後に加熱して焼結させた焼結体とした前記殺菌部材を製造する焼結工程と、を具備することを特徴とする。
本発明の殺菌部材の製造方法は、前記焼結工程において、前記粉末を電極間で加圧し、当該電極間にパルス通電を行うことによって発生した放電プラズマによって前記粉末を加熱する放電プラズマ焼結法を用いることを特徴とする。
本発明の殺菌部材の製造方法は、前記焼結工程において、焼結温度を２００℃以下とすることを特徴とする。
本発明の殺菌部材は、水素を含有する減圧雰囲気中においてＡｇで構成された銀母材に対してアーク放電を生じさせてＡｇを気化させてから微粒子として固化させるアークプラズマ強制蒸発法によって得られた平均粒径が１４ｎｍ〜１４４ｎｍの範囲である銀（Ａｇ）微粒子が、焼結されて構成された多孔質の焼結体であることを特徴とする。
The present invention has the following configurations in order to solve the above problems.
The method for producing a sterilizing member of the present invention is a method for producing a sterilizing member composed of silver (Ag) as a main component, and arcs with respect to a silver base material composed of Ag in a reduced pressure atmosphere containing hydrogen. A powder production step of producing Ag fine particles having an average particle size in the range of 14 nm to 144 nm by an arc plasma forced evaporation method in which an electric discharge is generated to vaporize Ag and then solidified as fine particles, and a powder composed of the Ag fine particles. It is characterized by comprising a sintering step of manufacturing the sterilizing member as a sintered body obtained by pressurizing, molding, and then heating and sintering.
The method for producing a sterilizing member of the present invention is a discharge plasma sintering method in which the powder is pressurized between electrodes and the powder is heated by discharge plasma generated by applying a pulse to the electrodes in the sintering step. Is characterized by using.
The method for producing a sterilizing member of the present invention is characterized in that the sintering temperature is set to 200 ° C. or lower in the sintering step.
The sterilizing member of the present invention is obtained by an arc plasma forced evaporation method in which an arc discharge is generated in a silver base material composed of Ag in a reduced pressure atmosphere containing hydrogen to vaporize the Ag and then solidify it as fine particles. It is characterized in that silver (Ag) fine particles having an average particle size in the range of 14 nm to 144 nm are a porous sintered body formed by sintering.
本発明は以上のように構成されているので、Ａｇを主材料とし、高い殺菌効果を有し、かつ製造が容易な殺菌部材を得ることができる。 Since the present invention is configured as described above, it is possible to obtain a sterilizing member which uses Ag as a main material, has a high sterilizing effect, and is easy to manufacture.
以下、本発明の実施の形態に係る殺菌部材、その製造方法について説明する。この殺菌部材は殺菌効果を有する銀（Ａｇ）で構成され、特にＡｇ粉末（Ａｇ微粒子）を原材料として製造される。 Hereinafter, the sterilizing member according to the embodiment of the present invention and the manufacturing method thereof will be described. This sterilizing member is composed of silver (Ag) having a bactericidal effect, and is particularly produced using Ag powder (Ag fine particles) as a raw material.
ここで原材料として用いられるＡｇ粉末はアークプラズマ強制蒸発法によって製造され、峯田才寛、齋藤達也、吉原崇裕、佐藤裕之、「アークプラズマ強制蒸発法によるＡｇナノパウダーの作成及び粉末特性評価」、日本金属学会誌（２０１９年）、第８３巻、第４号、１１９頁、あるいは、Ｔａｋａｈｉｒｏ Ｍｉｎｅｔａ、Ｔｅｔｓｕｙａ Ｓａｉｔｏ、Ｔａｋａｈｉｒｏ Ｙｏｓｈｉｈａｒａ ａｎｄ Ｈｉｒｏｙｕｋｉ Ｓａｔｏ、「Ｐｒｅｐｅｒａｔｉｏｎ ｏｆ Ｓｉｌｖｅｒ Ｎａｎｏｐａｒｔｉｃｌｅｓ ｂｙ Ａｒｃ Ｐｌａｓｍａ Ｍｅｔｈｏｄ ａｎｄ Ｔｈｅｉｒ Ｐｒｏｐｅｒｔｉｅｓ」、Ｍａｔｅｒｉａｌｓ Ｔｒａｎｓａｃｔｉｏｎｓ（２０１９年３月）、Ｖｏｌ．６０、Ｎｏ．４、５６９頁に記載されたものと同様である。このためのＡｇ粉末製造装置１の構成を模式的に図１に示す。ここで、タングステン電極（負極）１１と、炭素電極（正極）１２が放電用チャンバー１０中に設けられ、炭素電極１２上にターゲットとなるＡｇ母材２０が配置され、真空ポンプ１３によって排気される。Ａｇ母材２０は溶融銀で構成される。 The Ag powder used as a raw material here is produced by the arc plasma forced evaporation method, and is produced by Toshihiro Mineda, Tatsuya Saito, Takahiro Yoshihara, Hiroyuki Sato, "Preparation of Ag nanopowder by forced evaporation of arc plasma and evaluation of powder characteristics", Japan metal Journal (2019), No. 83 Volume, No. 4, page 119, or, Takahiro Mineta, Tetsuya Saito, Takahiro Yoshihara and Hiroyuki Sato, "Preperation of Silver Nanoparticles by Arc Plasma Method and Their Properties", Materials Transactions ( March 2019), Vol. 60, No. It is the same as that described on pages 4, 569. The configuration of the Ag powder production apparatus 1 for this purpose is schematically shown in FIG. Here, the tungsten electrode (negative electrode) 11 and the carbon electrode (positive electrode) 12 are provided in the discharge chamber 10, the target Ag base material 20 is arranged on the carbon electrode 12, and the gas is exhausted by the vacuum pump 13. .. The Ag base material 20 is made of molten silver.
一方、放電用チャンバー１０には、Ａｒ−Ｈ２（５０％）混合ガスが導入される。また、タングステン電極１１と炭素電極１２には電源１４が接続され、放電用チャンバー１０内の圧力が所定の範囲となり、電極間に高電圧が印加された場合にこれらの間でアーク放電が発生する。炭素電極１２は、実際にはこの際にＡｇ母材２０の表面を介してアーク放電が発生するように構成され、例えば、銅電極の上に炭素坩堝が配置され、この炭素坩堝内にＡｇ母材２０が配置されるように構成される。このため、アーク放電によってＡｇ母材２０からＡｇが蒸発し、その後に蒸発したＡｇ成分が固化して微粒子（Ａｇ微粒子）となる。この際、この雰囲気においては酸素（大気）は真空ポンプ１３により除去され、かつ混合ガスには還元性のガスであるＨ２が含まれるため、Ａｇ微粒子に酸素が取り込まれること、あるいはＡｇ微粒子表面に酸化膜が形成されることは抑制される。 On the other hand, an Ar—H 2 (50%) mixed gas is introduced into the discharge chamber 10. Further, a power supply 14 is connected to the tungsten electrode 11 and the carbon electrode 12, the pressure in the discharge chamber 10 is within a predetermined range, and when a high voltage is applied between the electrodes, an arc discharge is generated between them. .. The carbon electrode 12 is actually configured so that an arc discharge is generated through the surface of the Ag base material 20 at this time. For example, a carbon crucible is arranged on the copper electrode, and the Ag mother is placed in the carbon crucible. The material 20 is configured to be arranged. Therefore, Ag is evaporated from the Ag base material 20 by the arc discharge, and then the evaporated Ag component is solidified into fine particles (Ag fine particles). At this time, in this atmosphere, oxygen (atmosphere) is removed by the vacuum pump 13, and since the mixed gas contains H 2 which is a reducing gas, oxygen is taken into the Ag fine particles, or the surface of the Ag fine particles The formation of an oxide film is suppressed.
混合ガスは、放電用チャンバー１０と接続された捕集用チャンバー１５側に流れ、循環ポンプ１６によって排気され、循環されて再び放電用チャンバー１０に導入される。この際、Ａｇ微粒子は、混合ガスと共に捕集用チャンバー１５内部に設けられたフィルター１７中をこの混合ガスと共に流れ、この際にＡｇ微粒子のみがフィルター１７に捕集される。このように捕集されたＡｇ微粒子が前記のＡｇ粉末となる。なお、実際には放電用チャンバー１０、捕集用チャンバー１５は冷却水によって冷却され、冷却水の温度が一定に制御されることによって、放電用チャンバー１０、捕集用チャンバー１５の温度が制御される。 The mixed gas flows to the collection chamber 15 side connected to the discharge chamber 10, is exhausted by the circulation pump 16, is circulated, and is introduced into the discharge chamber 10 again. At this time, the Ag fine particles flow together with the mixed gas in the filter 17 provided inside the collection chamber 15, and at this time, only the Ag fine particles are collected by the filter 17. The Ag fine particles collected in this way become the Ag powder. Actually, the discharge chamber 10 and the collection chamber 15 are cooled by the cooling water, and the temperature of the cooling water is controlled to be constant, so that the temperatures of the discharge chamber 10 and the collection chamber 15 are controlled. To.
このように製造されたＡｇ粉末の特性、例えば平均粒径は、アーク放電の放電電流（電源１４）等によって調整が可能であり、例えばこの電流を４０〜１００Ａの範囲とすることにより、平均粒径を１４ｎｍ〜１４４ｎｍ程度に調整することができる。上記の構成により、このように平均粒径が小さく、酸素の混入が抑制されたＡｇ微粒子が得られる（粉末生成工程）。 The characteristics of the Ag powder thus produced, for example, the average particle size, can be adjusted by the discharge current of the arc discharge (power supply 14) or the like. For example, by setting this current in the range of 40 to 100 A, the average grain size The diameter can be adjusted to about 14 nm to 144 nm. With the above configuration, Ag fine particles having such a small average particle size and suppressed oxygen contamination can be obtained (powder production step).
このように製造されたＡｇ粉末が圧縮、成形後に焼結された焼結体が、多孔質の電極となる。この焼結を行うためには、例えば周知の放電プラズマ焼結法法（ＳＰＳ：Ｓｐａｒｋ Ｐｌａｓｍａ Ｓｉｎｔｅｒｉｎｇ）を用いることができる。ＳＰＳにおける装置構成は、例えば株式会社エヌジェーエスＳＰＳセンターのＨＰ（ＵＲＬ：ｈｔｔｐ：／ｗｗｗ．ｎｊｓ−ｊａｐａｎ．ｃｏ．ｊｐ／ｗｈａｔｓｓｐｓ．ｈｔｍｌ）に記載されている。ＳＰＳにおいては、ダイの内部に充填された粉末が上下のパンチによって上下方向で一軸加圧されると同時に、パンチ間で通電が行われることによって加熱が行われる。ＳＰＳにおいては、焼結助剤を用いることなしに粒成長を抑制した高密度焼結が可能である。ＳＰＳにおいては、Ａｇ粉末がダイの内部で高圧で一軸加圧された状態で、パルス電流が流されることによる放電によってＡｇ粉末が加熱されて焼結される（焼結工程）。 The sintered body obtained by compressing and molding the Ag powder thus produced and then sintering is a porous electrode. For this sintering, for example, a well-known discharge plasma sintering method (SPS: Spark Plasma Sintering) can be used. The device configuration in the SPS is described, for example, on the website of NGS SPS Center Co., Ltd. (URL: http: /www.njs-japan.co.jp/hatsps.html). In the SPS, the powder filled inside the die is uniaxially pressurized in the vertical direction by the upper and lower punches, and at the same time, heating is performed by energizing between the punches. In SPS, high-density sintering in which grain growth is suppressed is possible without using a sintering aid. In the SPS, the Ag powder is uniaxially pressurized at a high voltage inside the die, and the Ag powder is heated and sintered by a discharge caused by a pulse current (sintering step).
この際、峯田才寛、齋藤達也、吉原崇裕、佐藤裕之、「アークプラズマ強制蒸発法によるＡｇナノパウダーの作成及び粉末特性評価」、日本金属学会誌（２０１９年）、第８３巻、第４号、１１９頁に記載されたように、上記のＡｇ微粒子は、他の方法で製造されたＡｇ粒子と比べて、酸素等の不純物の混入が極めて少なく、結晶粒径が一様に小さな多結晶である。このため、このＡｇ微粒子を用いて、焼結助剤を添加することなく、Ａｇの焼結体を得ることができる。この焼結体を、元のＡｇ微粒子の形態を反映した多孔質とすることができ、これによってＡｇの実効的な表面積を大きくすることができ、殺菌効果を高くすることができる。以下に、このような実施例について説明する。 At this time, Toshihiro Mineda, Tatsuya Saito, Takahiro Yoshihara, Hiroyuki Sato, "Preparation of Ag Nanopowder by Arc Plasma Forced Evaporation Method and Evaluation of Powder Characteristics", Journal of the Japan Institute of Metals (2019), Vol. 83, No. 4. As described on page 119, the above-mentioned Ag fine particles are polycrystals having extremely small contamination of impurities such as oxygen and uniformly small crystal grain sizes as compared with Ag particles produced by other methods. is there. Therefore, using these Ag fine particles, it is possible to obtain a sintered body of Ag without adding a sintering aid. The sintered body can be made porous reflecting the morphology of the original Ag fine particles, whereby the effective surface area of Ag can be increased and the bactericidal effect can be enhanced. Such an embodiment will be described below.
ここで用いられたＡｇ粉末は前記のように製造され、その平均粒径は７８ｎｍとされた。その後、このＡｇ粉末の加圧、成形及び焼結は前記のようにＳＰＳを用いて行われ、印加圧力は６０ＭＰａ、焼結保持時間は１ｍｉｎとされ、焼結体の形状は直系１０ｍｍの円形とされた。また、焼結温度は１２７℃、３２７℃、５２７℃の３種類とされた。この場合における焼結温度とは、前記のダイ中に埋め込まれた熱電対で測定された温度である。この焼結体の表面のＳＥＭ（走査型電子顕微鏡）写真を図２（ａ：焼結温度１２７℃、ｂ：同３２７℃、ｃ：同５２７℃）に示す。焼結温度が低いほど原材料となったＡｇ微粒子の構造を反映した微細な凹凸が顕著に存在する。図２には、測定された密度（ｇ／ｃｍ３）も記載されている。このような微細構造を反映し、焼結温度が低いほど密度が低くなっている。 The Ag powder used here was produced as described above, and its average particle size was 78 nm. After that, pressurization, molding and sintering of this Ag powder are performed using SPS as described above, the applied pressure is 60 MPa, the sintering holding time is 1 min, and the shape of the sintered body is a circular shape of a direct line of 10 mm. Was done. The sintering temperatures were set to 127 ° C., 327 ° C., and 527 ° C. The sintering temperature in this case is the temperature measured by the thermocouple embedded in the die. An SEM (scanning electron microscope) photograph of the surface of the sintered body is shown in FIG. 2 (a: sintering temperature 127 ° C., b: 327 ° C., c: 527 ° C.). The lower the sintering temperature, the more fine irregularities that reflect the structure of the Ag fine particles used as the raw material are present. FIG. 2 also shows the measured density (g / cm 3 ). Reflecting such a fine structure, the lower the sintering temperature, the lower the density.
この焼結体に対して、グラム陰性菌であるＥｓｃｈｅｒｉｃｈｉａ ｃｏｌｉを用い、フィルム密着法（ＪＩＳＺ２８０１にほぼ準拠）を用いて抗菌性試験が行われた。ここでは、この菌の菌数が１０１０ｃｆｕ／ｍｌとなるように培養された菌液を２００倍に希釈した菌液が用いられた。上記の焼結体に対して表面を電解研磨し、更にアルコールと紫外線照射による滅菌処理を施して評価用の試料とし、この試料に対して、この菌液を５０μＬ滴下し、滅菌処理済みの直径８ｍｍの被覆フィルムを被せて試料上の全域に菌液を広げ、この状態で温度３５℃で０．５ｈ、１ｈ、２ｈ保持をした後の菌の量が評価された。また、比較用の試料として、図１のＡｇ母材２０と同一の銀が同様の形状に加工されて用いられた。この比較用の試料は、稠密なＡｇで構成されたものと考えることができる。 An antibacterial test was carried out on this sintered body using Escherichia coli, which is a Gram-negative bacterium, and a film adhesion method (almost compliant with JISZ2801). Here, a bacterial solution obtained by diluting the bacterial solution cultured so that the number of the bacteria was 10 10 cfu / ml was 200-fold was used. The surface of the above sintered body is electropolished and then sterilized by irradiation with alcohol and ultraviolet rays to prepare a sample for evaluation. 50 μL of this bacterial solution is dropped onto this sample to obtain a sterilized diameter. The amount of bacteria was evaluated after covering the sample with an 8 mm coating film and spreading the bacterial solution over the entire area and holding the sample at a temperature of 35 ° C. for 0.5 h, 1 h, and 2 hours. Further, as a sample for comparison, the same silver as the Ag base material 20 of FIG. 1 was processed into the same shape and used. This comparative sample can be considered to be composed of dense Ag.
菌の量の評価のために、上記のように保持後の試料から、ＳＣＤ（ソイビーン・カゼイン・ダイジェスト）培地に対してＬ（レシチン）、Ｐ（ポリソルベート８０）が添加されたＳＣＤＬＰ培地で構成された洗い出し液１０ｍｌを用いて、菌が回収された。その後、この洗い出し液１ｍｌを生理食塩水を用いて１０倍、１００倍、１０００倍、１００００倍に希釈した希釈液が作成された。その後、これらの各液に対して普通ブイヨン培地が混合されることによって固化後に、温度３５℃で４０〜４８ｈの間で培養が行われた。その後、確認された培地上の集落数から、各試料における生菌率が算出された。ここで、集落が確認されなかった試料に対しては試料全体に対して集落数が１であったものとし、この場合が測定の下限値に対応する。 In order to evaluate the amount of bacteria, the sample after retention as described above was composed of SCDLP medium in which L (lecithin) and P (polysorbate 80) were added to SCD (soybean casein digest) medium. Bacteria were recovered using 10 ml of the wash-out solution. Then, 1 ml of this wash-out solution was diluted 10-fold, 100-fold, 1000-fold, and 10000-fold with physiological saline to prepare a diluted solution. Then, after solidification by mixing a normal bouillon medium with each of these solutions, culturing was carried out at a temperature of 35 ° C. for 40 to 48 hours. After that, the viable cell rate in each sample was calculated from the confirmed number of colonies on the medium. Here, it is assumed that the number of colonies is 1 for the entire sample for the sample in which no colonies are confirmed, and this case corresponds to the lower limit value of the measurement.
使用された菌であるＥｓｃｈｅｒｉｃｈｉａ ｃｏｌｉの図２と同様の倍率で撮影されたＳＥＭ写真より、この菌は図２で示された各焼結体の微細構造における小孔よりも十分に大きいことが確認された。このため、この菌が焼結体内部に補足されたために洗い出し液に回収されなかった確率は低いと考えられる。このため、上記の処理における洗い出し液中の菌の量の初期値からの減少は、試料による殺菌効果を反映すると考えられる。 From the SEM photograph of Escherichia coli, which was used, taken at the same magnification as in FIG. 2, it was confirmed that this bacterium was sufficiently larger than the small pores in the microstructure of each sintered body shown in FIG. Was done. Therefore, it is considered that the probability that this bacterium was not recovered in the washout liquid because it was trapped inside the sintered body is low. Therefore, it is considered that the decrease in the amount of bacteria in the washout solution from the initial value in the above treatment reflects the bactericidal effect of the sample.
図３は、生菌率の保持時間依存性を試料毎に測定した結果であり、ここでは、前記の比較用試料と、焼結温度が１２７℃、３２７℃、５２７℃の３種類とされた計４種類の試料における結果が示されている。前記のように、洗い出し液に対する希釈率の異なる希釈液が評価のために用いられたが、生菌率は、同一の試料において各希釈液に対して希釈率が考慮された上で算出されている。ここで、生菌率２．５３×１０−７という値が前記のように集落が全く見られなかった場合に対応し、測定下限値に対応する。また、図４は、この結果より、生菌率が１／１０となる時間を図３における各試料毎に算出した結果である。 FIG. 3 shows the results of measuring the retention time dependence of the viable cell rate for each sample. Here, the above-mentioned comparative sample and the sintering temperature of 127 ° C., 327 ° C., and 527 ° C. were set. Results for a total of four samples are shown. As described above, diluents having different dilution ratios with respect to the washout solution were used for evaluation, but the viable cell ratio was calculated after considering the dilution ratio for each diluent in the same sample. There is. Here, the viable cell rate of 2.53 × 10-7 corresponds to the case where no colony is observed as described above, and corresponds to the lower limit of measurement. Further, FIG. 4 is a result of calculating the time for the viable cell ratio to be 1/10 for each sample in FIG. 3 from this result.
この結果より、保持時間と共に生菌率が減少するという殺菌効果はＡｇで構成された全ての試料で確認でき、ＡｇあるいはＡｇイオンに殺菌効果があることが認められる。しかしながら、上記の焼結体（焼結温度が１２７℃、３２７℃、５２７℃）においては生菌率の減少が、稠密なＡｇで構成された比較用試料よりも顕著であり、上記の焼結体は、比較用試料よりも高い殺菌効果を有する。また、上記の焼結体の中では、焼結温度が低いほど高い殺菌効果が認められ、焼結温度が１２７℃の場合に最も高い殺菌効果が得られる。この結果は、図２に示された微細構造を反映し、多孔質構造が顕著となる１２７℃の場合には、これによってＡｇの実効的な表面積が大きくなったことに起因する。 From this result, the bactericidal effect that the viable cell rate decreases with the retention time can be confirmed in all the samples composed of Ag, and it is confirmed that Ag or Ag ions have a bactericidal effect. However, in the above-mentioned sintered body (sintering temperature is 127 ° C., 327 ° C., 527 ° C.), the decrease in viable cell rate is remarkable as compared with the comparative sample composed of dense Ag, and the above-mentioned sintering The body has a higher bactericidal effect than the comparative sample. Further, among the above-mentioned sintered bodies, the lower the sintering temperature, the higher the bactericidal effect is recognized, and when the sintering temperature is 127 ° C., the highest bactericidal effect can be obtained. This result reflects the microstructure shown in FIG. 2 and is due to the fact that in the case of 127 ° C. where the porous structure becomes prominent, this increases the effective surface area of Ag.
また、上記のフィルム密着法以外の方法として、ハロー法（ＪＩＳＬ１９０２にほぼ準拠）によっても、上記の試料（比較用の試料を除く）が評価された。ハロー法においては、上記と同様の試験菌を含んだ寒天培地上に円形の試料が貼付され、２４〜４８時間培養後における菌の生育阻止帯（ハロー）の幅が評価される。ハローは、試料の殺菌効果によって生成され、試料周囲の環状の領域として認識され、その幅が大きいほど殺菌効果が高いことを意味する。図５は、このようなハローの幅を３種類の試料（焼結温度が１２７℃、３２７℃、５２７℃）に対して測定した結果である。この結果においても、焼結温度が低いほどハローの幅が大きくなることが確認され、上記と同様に、焼結温度が低いほど高い殺菌効果が得られることが明らかである。 Further, as a method other than the above-mentioned film adhesion method, the above-mentioned sample (excluding the sample for comparison) was also evaluated by the halo method (almost conforming to JIS L1902). In the halo method, a circular sample is attached on an agar medium containing the same test bacteria as described above, and the width of the bacterial growth inhibition zone (halo) after culturing for 24 to 48 hours is evaluated. The halo is generated by the bactericidal effect of the sample and is recognized as an annular region around the sample, and the larger the width, the higher the bactericidal effect. FIG. 5 shows the results of measuring the width of such a halo for three types of samples (sintering temperature is 127 ° C., 327 ° C., 527 ° C.). Also in this result, it was confirmed that the lower the sintering temperature, the wider the width of the halo, and it is clear that the lower the sintering temperature, the higher the bactericidal effect.
以上より、上記のＡｇ粉末を原材料とした焼結体を、殺菌部材として使用することができる。上記のＡｇ粉末（Ａｇ微粒子）を用いた場合には、焼結を低温で行うことができ、これによって特にＡｇの実効的な表面積が大きな多孔質の焼結体を得ることができ、特に殺菌効果の高い殺菌部材を得ることができる。焼結温度は、２００℃以下とすることが特に好ましいが、焼結温度が５２７℃の場合においても、比較用の試料よりも高い殺菌効果が得られる。 From the above, the sintered body made from the above Ag powder as a raw material can be used as a sterilizing member. When the above-mentioned Ag powder (Ag fine particles) is used, sintering can be performed at a low temperature, whereby a porous sintered body having a particularly large effective surface area of Ag can be obtained, and particularly sterilization. A highly effective sterilizing member can be obtained. The sintering temperature is particularly preferably 200 ° C. or lower, but even when the sintering temperature is 527 ° C., a higher bactericidal effect than that of the comparative sample can be obtained.
なお、上記の殺菌部材の製造方法において、焼結工程では放電プラズマ焼結法（ＳＰＳ）が用いられた。しかしながら、上記のようなＡｇ粉末によって多孔質の焼結体が得られる限りにおいて、他の方法を焼結工程で用いてもよい。例えば、このＡｇ粉末を加圧した圧粉体を製造し、この圧粉体を電気炉中で熱処理することによって焼結体としてもよい。こうした場合であっても、上記のＡｇ粉末を用いた場合には、低温で多孔質の焼結体を得ることができ、同様に殺菌効果が高い焼結体（殺菌部材）を得ることができる。 In the above-mentioned method for manufacturing a sterilizing member, a discharge plasma sintering method (SPS) was used in the sintering step. However, other methods may be used in the sintering step as long as a porous sintered body can be obtained from the Ag powder as described above. For example, a green compact obtained by pressurizing this Ag powder may be produced, and the green compact may be heat-treated in an electric furnace to form a sintered body. Even in such a case, when the above Ag powder is used, a porous sintered body can be obtained at a low temperature, and a sintered body (sterilizing member) having a high sterilizing effect can be obtained as well. ..
１ Ａｇ粉末製造装置
１０ 放電用チャンバー
１１ タングステン電極（負極）
１２ 炭素電極（正極）
１３ 真空ポンプ
１４ 電源
１５ 捕集用チャンバー
１６ 循環ポンプ
１７ フィルター
２０ Ａｇ母材
1 Ag powder production equipment 10 Discharge chamber 11 Tungsten electrode (negative electrode)
12 Carbon electrode (positive electrode)
13 Vacuum pump 14 Power supply 15 Collection chamber 16 Circulation pump 17 Filter 20 Ag Base material
Claims (4)
水素を含有する減圧雰囲気中においてＡｇで構成された銀母材に対してアーク放電を生じさせてＡｇを気化させてから微粒子として固化させるアークプラズマ強制蒸発法によって平均粒径が１４ｎｍ〜１４４ｎｍの範囲であるＡｇ微粒子を生成する粉末生成工程と、
前記Ａｇ微粒子で構成された粉末を加圧、成形した後に加熱して焼結させた焼結体とした前記殺菌部材を製造する焼結工程と、
を具備することを特徴とする殺菌部材の製造方法。 It is a method for manufacturing a sterilizing member composed of silver (Ag) as a main component.
The average particle size is in the range of 14 nm to 144 nm by the arc plasma forced evaporation method in which an arc discharge is generated in a silver base material composed of Ag in a reduced pressure atmosphere containing hydrogen to vaporize the Ag and then solidify it as fine particles. The powder generation process for producing Ag fine particles, which is
A sintering step of producing the sterilizing member as a sintered body obtained by pressurizing and molding a powder composed of the Ag fine particles and then heating and sintering the powder.
A method for manufacturing a sterilizing member, which comprises the above.
前記粉末を電極間で加圧し、当該電極間にパルス通電を行うことによって発生した放電プラズマによって前記粉末を加熱する放電プラズマ焼結法を用いることを特徴とする請求項１に記載の殺菌部材の製造方法。 In the sintering process
The sterilizing member according to claim 1, wherein a discharge plasma sintering method is used in which the powder is pressurized between the electrodes and the powder is heated by the discharge plasma generated by applying a pulse to the electrodes. Production method.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS569304A (en) * | 1979-07-06 | 1981-01-30 | Natl Res Inst For Metals | Manufacture of fine metal particle |
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| JPS569304A (en) * | 1979-07-06 | 1981-01-30 | Natl Res Inst For Metals | Manufacture of fine metal particle |
| JPS58104103A (en) * | 1981-12-17 | 1983-06-21 | Natl Res Inst For Metals | Method and device for producing fine metallic particle |
| JPS60162705A (en) * | 1984-02-03 | 1985-08-24 | Natl Res Inst For Metals | Production of ultrafine metallic particles |
| JP2007506545A (en) * | 2003-09-24 | 2007-03-22 | ナノテクノロジーズ、インコーポレイテッド | Nanopowder synthesis using pulsed arc discharge and applied magnetic field |
| KR20060068473A (en) * | 2004-12-16 | 2006-06-21 | 코스모스티이에스 (주) | Sintered body containing silver fine particles |
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| 峯田才寛 他: "アークプラズマ強制蒸発法によるＡｇナノパウダーの作製及び粉末特性評価", 日本金属学会誌, vol. 第８３巻第４号, JPN6022052536, 1 April 2019 (2019-04-01), JP, pages 119 - 123, ISSN: 0004942426 * |
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