JP4424913B2 - Antibacterial treatment method by thermal spraying of plastic products - Google Patents
Antibacterial treatment method by thermal spraying of plastic products Download PDFInfo
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- JP4424913B2 JP4424913B2 JP2003031324A JP2003031324A JP4424913B2 JP 4424913 B2 JP4424913 B2 JP 4424913B2 JP 2003031324 A JP2003031324 A JP 2003031324A JP 2003031324 A JP2003031324 A JP 2003031324A JP 4424913 B2 JP4424913 B2 JP 4424913B2
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- 239000004033 plastic Substances 0.000 title claims description 47
- 238000000034 method Methods 0.000 title claims description 33
- 230000000844 anti-bacterial effect Effects 0.000 title claims description 26
- 238000007751 thermal spraying Methods 0.000 title claims description 12
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 35
- 229910052709 silver Inorganic materials 0.000 claims description 33
- 239000004332 silver Substances 0.000 claims description 33
- 239000003242 anti bacterial agent Substances 0.000 claims description 28
- 239000002245 particle Substances 0.000 claims description 28
- 238000005507 spraying Methods 0.000 claims description 14
- 239000011246 composite particle Substances 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 5
- 239000000463 material Substances 0.000 description 10
- 239000000843 powder Substances 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 239000007921 spray Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 238000010285 flame spraying Methods 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 239000004599 antimicrobial Substances 0.000 description 2
- 238000005422 blasting Methods 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241000588724 Escherichia coli Species 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 241000219094 Vitaceae Species 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000000843 anti-fungal effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000567 combustion gas Substances 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
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 235000021021 grapes Nutrition 0.000 description 1
- 230000009036 growth inhibition Effects 0.000 description 1
- 238000011081 inoculation Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 238000010137 moulding (plastic) Methods 0.000 description 1
- 239000011224 oxide ceramic Substances 0.000 description 1
- 229910052574 oxide ceramic Inorganic materials 0.000 description 1
- 238000007750 plasma spraying Methods 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 238000005480 shot peening Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Images
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- Application Of Or Painting With Fluid Materials (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Coating By Spraying Or Casting (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、プラスチック製品の溶射による抗菌処理方法に関するものである。
【０００２】
【従来の技術】
抗菌をうたったプラスチック製品は多種多様にわたっているが、その殆どは、イオン化しやすい金属粒子を抗菌剤としてプラスチック材料中に混合したものであるから、抗菌剤はプラスチック製品全体に分散された状態にある。しかし抗菌性は、表面だけが受け持つ性能であるので、プラスチック製品全体に抗菌剤が分散された状態では、抗菌性能も十分ではなく、また抗菌剤の分量も多量に必要となるので高価になるという欠点がある。
【０００３】
これに対して、特開平９−１００２０５号、同６−２４６７７３号の発明ではプラスチックの成形用金型表面に、銀ゼオライトのような抗菌剤を予めコートしておき、成形製品表面に転写するという技術を提案している。しかしプラスチック製品表面に対する転写がどの程度になされるか不明であり、また付着した抗菌剤がいつまで剥離せずにいられるかについても疑問が残る。
【０００４】
さらに、特開平９−１２４４２４号の発明では、粒子表面を無電解メッキ法により抗菌防黴性を有する金属で被膜した組成物を開示している。この場合、組成物を塗料として使用することが可能であり、プラスチック製品全体に分散するような無駄は避けることができる。しかしながら、プラスチック製品の場合には表面に塗装をするということが少なく、従って特殊なケースを除いてはあまり有効であるとは思えない。しかもまた、この場合抗菌剤の保持力は塗料のプラスチック表面への付着力によって左右されることになり、塗装が剥れてしまえば、効果はなくなる。
【０００５】
【発明が解決しようとする課題】
本発明は前記の点に着目してなされたものであり、その課題はプラスチック製品の表面に、必要十分な量及び強度にて抗菌剤を固定できるようにすることである。また本発明の他の課題は、一定量の抗菌剤で一定の抗菌性能が確実に保証されるプラスチック製品を提供できるようにすることである。
【０００６】
前記の課題を解決するため、本発明は、プラスチック製品に対する抗菌処理のための方法として、溶射法によって抗菌剤の粒子を、プラスチック製品の表面にまばらに打ち込まれ、その内のあるものは表面から一部が外に出、あるものは浅く或いは深く入って外部と通じるような状態になっているものとするという手段を講じたものである。
【０００７】
抗菌剤をプラスチック製品の表面に固定する溶射法としては幾つかの方法がある。例えば、燃焼ガスを熱源とするフレーム溶射、高速フレーム溶射、爆発溶射の各方法、電気を熱源とするアーク溶射その他の各種のプラズマ溶射方法、レーザー光線を熱源にする場合のレーザー溶射方法、その他には、コールドスプレー法、熱源を必要としない方法としてショットピーニングのようなブラスト法等様々な溶射方法がある。本発明の場合これらのほぼすべての方法を適用することが可能である。しかし一長一短があるので、どのような溶射法も適用できるとしても、本発明の場合には粒子の飛行速度が極めて速く、かつ温度が低い溶射法として高速フレーム溶射法が最適である。またコールドスプレー法も好適であるが、数千万円以上の設備投資を必要とする。また室温ブラスト法は低コストで実施可能であるので実用的である。
【０００８】
抗菌剤は、微生物及び超微生物の破壊又は成長阻害を起こす化学物質のことであり、例えば銀、銅、亜鉛その他の金属が用いられる。これらの金属は単独で、或いは他の物質との混合物として使用され、本発明については特に銀、或いは銀と他の物質との混合粉の形で使用される。
【０００９】
抗菌剤をプラスチック製品の表面に固定する方法の第１としては、溶射法によって抗菌剤の粒子を、プラスチック製品の表面にまばらに打ち込む方法がある。この方法１によって溶射処理されたプラスチック表面の状態を模式的に示せば図１のようになる。図１は約２００倍の倍率で観察した顕微鏡像であり、銀粒子、又は金属を除く他の物質と銀との混合物を造粒した銀複合粒子の粒径は１５〜２５μｍである。なお、本発明おいて「まばらに」という場合は０．５ｍｍ×０．５ｍｍに１〜２個という程度の分布密度を言う。しかし最大粒径２５μｍというのは抗菌性能面での上限であり、これを越えても経済性が低下するだけである。
【００１０】
抗菌剤の使用形態は、銀粒子、或いは銀と他の物質例えばアルミナとの造粒粉である銀複合粒子の２形態である。後者の場合、他の物質には銀と混合し造粒されるすべての物質を適用可能であるが、溶射中に溶融し、銀と合金を作ってしまう金属は使用できない。酸化物セラミックスが主要な材料となる。前記の銀とアルミナの場合には、銀１重量部に対して、アルミナ５０重量部の比率でも十分な抗菌効果がある。なお銀以外の金属についても、ほぼ同様に取り扱うことができる。
【００１１】
また溶射法は成膜法の一つであるので、溶射装置において噴出する皮膜材料（抗菌剤の粒子）の分量も、成膜に必要な量となっている。しかし本発明における使用形態１では、成膜するほどの多量の材料を必要としないために、材料供給装置に若干の改造が必要である。また、プラスチック製品表面を溶射の熱にさらす時間を最小限に止めるために、溶射ガンの移動速度を早めに設定することも必要である。上の２点に留意することにより、すべての溶射装置を抗菌処理用として使用することが可能となる。
【００１２】
銀、或いは銀と他の物質との複合粒子を、本発明の抗菌処理方法によりプラスチック製品表面にまばらに打ち込んだ状態は図２に示したようになる。即ち、プラスチック製品の表面１１に銀、又はその複合物質の粒子１２がまばらに打ち込まれ、その内のあるものは表面から一部が外に出、あるものは浅く或いは深く入って外部と通じるような状態になる。
【００１３】
抗菌剤をプラスチック製品の表面に固定する方法の第２として、抗菌剤粒子とプラスチック粉末とを混合し、溶射法によってプラスチック製品表面に成膜する方法がある。この第２番目の形態でも、抗菌剤粒子には銀粒子或いは銀粒子と他の粒子との複合粒子を使用することができる。プラスチック粉末の材質は、本発明方法を実施するプラスチック製品と同じ材質であるか、或いは親和性の良い材質であることが望ましい。
【００１４】
抗菌剤の固定方法の第２は、プラスチック溶射法を本発明の方法に適用するために開発されたものである。プラスチック溶射法は本来は鉄鋼製品の表面にプラスチックを溶射、成膜して耐食性を付与することが目的であるが、本発明は抗菌剤をプラスチック製品表面に固定する手段としてプラスチック溶射法を応用している。抗菌剤は前記の銀粒子又は銀複合粒子であり、またその粒径も１５〜２５μｍの範囲で良い。この粒径に対しては、粒子１２とともに成膜されるプラスチック皮膜１３の厚さは２０〜３０μｍの範囲に設定することになる。ほとんどの粒子を皮膜１３から露出させるためであり、この状態を模式的に図示したのが図３である。なお、第２の固定方法における銀粒子又は銀複合粒子の粒径は皮膜の厚さとの関係から決められる相対的なものである。
【００１５】
特筆すべき点として、銀粒子又は銀複合粒子とプラスチック粉末との「濡れ性」の極めて良いことを指摘することができる。プラスチックが銀粒子又は銀複合粒子をしっかりと保持している状態は図３に示した通りであることが顕微鏡下に観察され、また後述するように耐久性の面でも確認されている。
【００１６】
【実施例】
１．銀粉末とアルミナ粉末とを重量比２０：８０で混合し造粒した銀複合粒子を用いて、ＰＰ、ＡＢＳなどを素材とするプラスチック製品の表面に、高速フレーム溶射法によって、約１秒間溶射し、１ｃｍ２当たり約４００個の密度で打ち込んだ。
【００１７】
得られた抗菌処理済みのプラスチック製品は、抗菌処理を経ないものと比較して外観的に差が殆んど分からなかった。すなわち表面の光沢は全く失われていない。また、ＪＩＳＺ２８０１に規定されている試験方法により抗菌性評価を行ったところ、本発明による処理後のプラスチック製品の抗菌性はもとより非の打ち所がなく、熱湯による３００回〜１０００回の洗浄後も黄色ぶどう状球菌、大腸菌とも、接種対象区には１０５〜１０６個の生菌があったにも拘らず１８時間経過後には夫々１０個以下となり、抗菌活性値は５．２以上を示した。
【００１８】
２．銀粉末とアルミナ粉末とを重量比１：５０で混合し造粒した直径２０μｍ銀複合粒子を用いて、５秒間溶射成膜し、膜厚約２０μｍの皮膜を形成し、１ｃｍ２当たり約３００個の密度で上記抗菌剤を固定した。
【００１９】
得られた抗菌処理済みのプラスチック製品は、成膜プラスチックの外観を持っている。また、実施例１と同法により抗菌性評価を行ったところ、実施例１と同等の抗菌効果を確認し、また熱湯による洗浄後も実施例１の場合とほぼ同等の抗菌性能を示すことが確認された。
【００２０】
【発明の効果】
本発明は以上の如く構成されかつ作用するものであるから、プラスチック製品の表面に、溶射によって、必要十分な量の抗菌剤を必要な強度で固定することができ、その結果、一定量の抗菌剤で一定の抗菌性能が確実に保証され、無駄がなく、最小限度のコストで最良の効果を期待することができるという効果を奏するものである。
【図面の簡単な説明】
【図１】本発明のプラスチック製品の溶射による抗菌処理方法を実施した、プラスチック製品表面における抗菌剤の分布状態を示す、倍率約２００倍の顕微鏡写真に基づく模式図。
【図２】請求項２記載の発明によりプラスチック製品表面に固定された、抗菌剤の状態を模式的に示す断面図。
【図３】請求項４記載の発明によりプラスチック製品表面に固定された、抗菌剤の状態を模式的に示す断面図。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an antibacterial treatment method by thermal spraying of plastic products.
[0002]
[Prior art]
There are a wide variety of plastic products that claim antibacterial properties, but most of them are metal particles that are easily ionized mixed in plastic materials as antibacterial agents, so the antibacterial agents are dispersed throughout the plastic products. . However, since antibacterial properties are the performance that only the surface is responsible for, the antibacterial performance is not sufficient when the antibacterial agent is dispersed throughout the plastic product, and the amount of the antibacterial agent is large, and it is expensive. There are drawbacks.
[0003]
On the other hand, in the inventions of JP-A-9-100205 and JP-A-6-246773, an antibacterial agent such as silver zeolite is coated in advance on the surface of a plastic molding die and transferred to the surface of the molded product. Proposing technology. However, it is unclear how much transfer to the surface of the plastic product is made, and there is a question as to how long the attached antibacterial agent can be kept without peeling.
[0004]
Furthermore, the invention of JP-A-9-124424 discloses a composition in which the particle surface is coated with a metal having antibacterial and antifungal properties by an electroless plating method. In this case, the composition can be used as a paint, and waste that is dispersed throughout the plastic product can be avoided. However, in the case of plastic products, it is rare to paint on the surface, so it seems unlikely to be effective except in special cases. Moreover, in this case, the retention of the antibacterial agent depends on the adhesion of the paint to the plastic surface, and if the coating is peeled off, the effect is lost.
[0005]
[Problems to be solved by the invention]
The present invention has been made paying attention to the above points, and its object is to make it possible to fix an antibacterial agent on the surface of a plastic product with a necessary and sufficient amount and strength. Another object of the present invention is to provide a plastic product that ensures a certain amount of antibacterial performance with a certain amount of antibacterial agent.
[0006]
In order to solve the above-mentioned problems, the present invention is a method for antibacterial treatment of plastic products, in which particles of antibacterial agents are sparsely injected onto the surface of plastic products by spraying , and some of them are exposed from the surface. partially go out, in which took measures that some are to be put into a state as to communicate with the shallow or deep entered by external.
[0007]
There are several thermal spraying methods for fixing an antibacterial agent to the surface of a plastic product. For example, flame spraying using combustion gas as a heat source, high-speed flame spraying, explosion spraying methods, arc spraying using electricity as a heat source, and other various plasma spraying methods, laser spraying methods using laser light as a heat source, etc. There are various spraying methods such as a cold spray method and a blasting method such as shot peening as a method which does not require a heat source. In the present invention, almost all of these methods can be applied. However, because there are advantages and disadvantages, even if any spraying method can be applied, in the case of the present invention, the high-speed flame spraying method is optimal as a spraying method in which the flying speed of particles is extremely high and the temperature is low. The cold spray method is also suitable, but requires capital investment of tens of millions of yen or more. The room temperature blasting method is practical because it can be carried out at low cost.
[0008]
An antibacterial agent is a chemical substance that causes destruction or growth inhibition of microorganisms and super microorganisms. For example, silver, copper, zinc, and other metals are used. These metals are used alone or as a mixture with other substances, and in the present invention, in particular, in the form of silver or a mixed powder of silver and other substances.
[0009]
As a first method of fixing the antibacterial agent to the surface of the plastic product, there is a method of sparsely injecting the particles of the antibacterial agent onto the surface of the plastic product by a thermal spraying method . The method 1 of this state of the thermal spray-treated plastic surface is shown in Figure 1 if Shimese schematically. FIG. 1 is a microscopic image observed at a magnification of about 200 times. The particle diameter of silver composite particles obtained by granulating silver particles or a mixture of silver and another substance other than metal is 15 to 25 μm. In the present invention, “sparsely” means a distribution density of about 1 to 2 in 0.5 mm × 0.5 mm. However, the maximum particle size of 25 μm is the upper limit in terms of antibacterial performance, and even if it exceeds this, the economic efficiency is only lowered.
[0010]
The antimicrobial agent is used in two forms: silver particles or silver composite particles which are granulated powder of silver and another substance such as alumina. In the latter case, all materials that are mixed with silver and granulated can be applied to other materials, but metals that melt during spraying to form an alloy with silver cannot be used. Oxide ceramics are the main material. In the case of the above-mentioned silver and alumina, there is a sufficient antibacterial effect even at a ratio of 50 parts by weight of alumina to 1 part by weight of silver. Note that metals other than silver can be handled in substantially the same manner.
[0011]
Further, since the thermal spraying method is one of the film forming methods, the amount of the coating material (antibacterial agent particles) ejected in the thermal spraying apparatus is also an amount necessary for the film forming. However, in the usage pattern 1 according to the present invention, since a large amount of material is not required to form a film, the material supply device needs to be slightly modified. It is also necessary to set the moving speed of the spray gun early in order to minimize the time during which the plastic product surface is exposed to the heat of spraying. By keeping the above two points in mind, it is possible to use all thermal spraying devices for antibacterial treatment.
[0012]
A state in which silver or composite particles of silver and other substances are sparsely applied to the surface of a plastic product by the antibacterial treatment method of the present invention is as shown in FIG. That is, silver or a
[0013]
As a second method of fixing the antibacterial agent to the surface of the plastic product, there is a method of mixing the antibacterial agent particles and the plastic powder and forming a film on the surface of the plastic product by a thermal spraying method . Also in the second embodiment of this, the antimicrobial agent particles can be used composite particles of silver particles or silver particles and other particles. The material of the plastic powder is preferably the same material as that of the plastic product for carrying out the method of the present invention or a material having good affinity.
[0014]
The second method for fixing the antibacterial agent was developed in order to apply the plastic spraying method to the method of the present invention. The plastic spraying method is originally intended to spray plastic on the surface of steel products and to form a film to give corrosion resistance. However, the present invention applies the plastic spraying method as a means to fix the antibacterial agent on the surface of plastic products. ing. The antibacterial agent is the above-mentioned silver particles or silver composite particles, and the particle size thereof may be in the range of 15 to 25 μm. For this particle size, the thickness of the
[0015]
It should be noted that the “wetting property” between the silver particles or the silver composite particles and the plastic powder is very good. It is observed under a microscope that the plastic holds the silver particles or the silver composite particles firmly as shown in FIG. 3, and has been confirmed in terms of durability as described later.
[0016]
【Example】
1. Using silver composite particles made by mixing and granulating silver powder and alumina powder at a weight ratio of 20:80, the surface of a plastic product made of PP, ABS or the like is sprayed for about 1 second by a high-speed flame spraying method. It was driven at a density of about 400 per cm 2 .
[0017]
The obtained plastic product after antibacterial treatment showed almost no difference in appearance as compared with the product not subjected to the antibacterial treatment. That is, the gloss of the surface is not lost at all. In addition, when the antibacterial property was evaluated by a test method defined in JISZ2801, the antibacterial property of the plastic product after the treatment according to the present invention was not limited, and it was in the form of yellow grapes after 300 to 1000 washings with hot water. aureus, both E. coli inoculation subject ku become respectively 10 or less after regardless 18 hours elapsed even had 105 to 106 viable bacteria, the antibacterial activity value was 5.2 or more.
[0018]
2. Using silver composite particles of 20 μm in diameter obtained by mixing and granulating silver powder and alumina powder at a weight ratio of 1:50, thermal spraying was performed for 5 seconds to form a film with a film thickness of about 20 μm, and about 300 particles per 1 cm 2. The antibacterial agent was fixed at the density of
[0019]
The obtained antibacterial treated plastic product has the appearance of a film-formed plastic. Moreover, when the antibacterial evaluation was performed by the same method as in Example 1, the antibacterial effect equivalent to that in Example 1 was confirmed, and the antibacterial performance equivalent to that in Example 1 was exhibited even after washing with hot water. confirmed.
[0020]
【The invention's effect】
Since the present invention is constructed and operates as described above, a necessary and sufficient amount of antibacterial agent can be fixed to the surface of a plastic product by spraying, and as a result, a certain amount of antibacterial agent can be obtained. The agent ensures certain antibacterial performance, has no waste, and has the effect that the best effect can be expected at a minimum cost.
[Brief description of the drawings]
FIG. 1 is a schematic diagram based on a microphotograph at a magnification of about 200 times showing a distribution state of an antibacterial agent on the surface of a plastic product in which an antibacterial treatment method by thermal spraying of the plastic product of the present invention is performed.
FIG. 2 is a cross-sectional view schematically showing the state of an antibacterial agent fixed on the surface of a plastic product according to the invention of claim 2;
FIG. 3 is a cross-sectional view schematically showing the state of an antibacterial agent fixed on the surface of a plastic product according to the invention of claim 4;
Claims (2)
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| JP2003031324A JP4424913B2 (en) | 2003-02-07 | 2003-02-07 | Antibacterial treatment method by thermal spraying of plastic products |
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| JP2008530352A (en) * | 2005-01-10 | 2008-08-07 | ジオム コーポレイション | Powder spray composition |
| US8753561B2 (en) * | 2008-06-20 | 2014-06-17 | Baxter International Inc. | Methods for processing substrates comprising metallic nanoparticles |
| AU2013252461A1 (en) * | 2012-04-24 | 2014-12-04 | Aereus Technologies Inc. | Coatings, coated surfaces, and methods for production thereof |
| CN107299312B (en) * | 2017-05-24 | 2019-04-12 | 昆明理工大学 | A method of enhancing hot-spraying coating antibacterial effect |
| CN113802083B (en) * | 2021-08-23 | 2024-01-30 | 昆明理工大学 | Preparation method of composite antibacterial coating |
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