JPH11302570A - Production of antimicrobial coating film - Google Patents
Production of antimicrobial coating filmInfo
- Publication number
- JPH11302570A JPH11302570A JP10753898A JP10753898A JPH11302570A JP H11302570 A JPH11302570 A JP H11302570A JP 10753898 A JP10753898 A JP 10753898A JP 10753898 A JP10753898 A JP 10753898A JP H11302570 A JPH11302570 A JP H11302570A
- Authority
- JP
- Japan
- Prior art keywords
- coating film
- aqueous solution
- silver
- antimicrobial
- antibacterial
- 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.)
- Pending
Links
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、抗菌性を有する塗
膜を製造する方法に関するものである。[0001] The present invention relates to a method for producing a coating film having antibacterial properties.
【０００２】[0002]
【従来技術及びその課題】特公平２−４０７５４号公報
には、塗膜に抗菌性を付与する方法として、有機系抗菌
剤を含有した塗膜を陽極酸化皮膜表面に形成することが
示されている。しかし、有機系抗菌剤はＶＯＣ規制等の
問題があり、また、有機系抗菌剤は即効性の点で優れて
いるが、持続性や安全性の点では無機系抗菌剤が優れて
いるので、無機系抗菌剤が主として使用されるようにな
ってきている。現在市販されている無機系抗菌剤として
は、抗菌成分である銀、銅、亜鉛等の金属の微粒子又は
イオンを、ゼオライト、リン酸ジルコニウム等の無機微
粒子に担持させたものがある。2. Description of the Related Art Japanese Patent Publication No. 2-40754 discloses a method for imparting antibacterial properties to a coating film by forming a coating film containing an organic antibacterial agent on the surface of an anodized film. I have. However, organic antibacterial agents have problems such as VOC regulations, and organic antibacterial agents are excellent in immediate effect, but inorganic antibacterial agents are excellent in sustainability and safety. Inorganic antibacterial agents are mainly used. Currently available inorganic antibacterial agents include those in which fine particles or ions of a metal such as silver, copper, and zinc, which are antibacterial components, are supported on inorganic fine particles such as zeolite and zirconium phosphate.
【０００３】ところで、これらの無機系抗菌剤を水性電
着塗料中に添加して塗膜を形成することによって塗膜に
抗菌性を付与する方法が、提案されている（特開平９−
１５７５５０号公報）。しかし、これらの無機系抗菌剤
は、一般に２〜１０μｍの大きさを有しており、小さい
ものでも０．３μｍの大きさを有しているので、電着塗
料中で沈降したり、塗膜内部に均一に析出しなかった
り、フィルターによって除去されたりしてしまい、それ
故、上記方法では、満足し得る抗菌性を有する塗膜を得
るのが困難であった。また、上記方法では、塗膜表面
に、ぶつぶつ、ざらつき等の不良も生じていた。Meanwhile, a method has been proposed in which an inorganic antibacterial agent is added to an aqueous electrodeposition coating material to form a coating film so as to impart antibacterial properties to the coating film (Japanese Patent Application Laid-Open No. H9-1997).
157550). However, these inorganic antibacterial agents generally have a size of 2 to 10 μm, and even small ones have a size of 0.3 μm. They were not uniformly deposited inside or were removed by a filter, and it was therefore difficult to obtain a coating film having satisfactory antibacterial properties by the above method. In addition, in the above-described method, defects such as bumps and roughness have occurred on the coating film surface.
【０００４】一方、銀コロイド溶液を用いて塗膜に抗菌
性を付与する方法も提案されている。例えば、焼成後の
塗膜表面に銀コロイド溶液を塗布した後、再度塗膜を焼
成する方法や、未焼成の塗膜表面に銀コロイド溶液を塗
布した後、塗膜を焼成する方法がある。しかし、銀コロ
イドは、安定性に欠け、しかも、コロイド自体が小さい
ものでも５〜２０ｎｍの大きさを有しているので、塗膜
を通過できるものが水等のイオンのレベルのものである
ことに鑑みると、銀コロイドが塗膜表面から塗膜内部へ
浸透するのは不可能であり、それ故、これらの方法で
は、銀の塗膜内部への拡散は熱拡散のみとなり、銀の拡
散量は非常に少ないものとなり、膜厚の大きな塗膜の下
部まで抗菌性を付与するのが困難であった。On the other hand, there has been proposed a method of imparting antibacterial properties to a coating film using a silver colloid solution. For example, there is a method in which a silver colloid solution is applied to the surface of a baked coating film and then the coating film is baked again, or a method in which a silver colloid solution is applied to an unfired coating film surface and then the coating film is baked. However, silver colloids lack stability and, even if the colloid itself is small, it has a size of 5 to 20 nm, so that what can pass through the coating film is at the level of ions such as water. In view of this, it is impossible for the silver colloid to penetrate from the surface of the coating to the inside of the coating. Therefore, in these methods, the diffusion of silver into the coating is only thermal diffusion, and the amount of silver diffusion Was very small, and it was difficult to impart antibacterial properties to the lower part of the coating film having a large thickness.
【０００５】本発明は、抗菌成分である銀又は銅が内部
に十分に且つ均一に分散してなる塗膜を得ることができ
る製造方法を提供することを目的とする。An object of the present invention is to provide a production method capable of obtaining a coating film in which silver or copper as an antibacterial component is sufficiently and uniformly dispersed therein.
【０００６】[0006]
【課題を解決するための手段】本発明は、抗菌性を有す
る塗膜を製造する方法において、未焼成の塗膜の表面
に、銀イオン又は銅イオンと還元剤とを含んでなる抗菌
水溶液を塗布し、その後、塗膜を焼成して銀イオン又は
銅イオンを還元することを特徴としている。According to the present invention, there is provided a method for producing a coating film having antibacterial properties, comprising the steps of: providing an antibacterial aqueous solution containing silver ions or copper ions and a reducing agent on the surface of an unfired coating film; It is characterized in that silver ions or copper ions are reduced by baking the coating film after application.
【０００７】抗菌性を有する塗膜は、母材の表面に直接
形成する場合に限るものではなく、母材表面に通常の方
法で形成し焼成した塗膜の表面に、形成してもよい。母
材としては、特に制限はないが、例えば、鉄、ステンレ
ス、アルミニウム、チタン等が用いられる。The coating film having antibacterial properties is not limited to the case where it is directly formed on the surface of the base material, but may be formed on the surface of the base material by a usual method and fired. Although there is no particular limitation on the base material, for example, iron, stainless steel, aluminum, titanium or the like is used.
【０００８】塗装の前処理としては、通常の塗装仕様を
そのまま適用できる。例えば、母材表面を、化成処理し
たり、陽極酸化処理したりしてもよい。また、母材に対
して前処理しなくてもよい。As a pretreatment for coating, ordinary coating specifications can be applied as they are. For example, the base material surface may be subjected to a chemical conversion treatment or an anodic oxidation treatment. Further, it is not necessary to preprocess the base material.
【０００９】塗膜を形成する塗料は、水性塗料に限る。
塗装方法は、電着、スプレー、浸漬、ロール、刷毛塗り
等のいずれの方法でもよい。なお、電着で行う場合に
は、塗料は、アニオン樹脂系、カチオン樹脂系のいずれ
でもよい。[0009] The paint for forming the coating film is limited to a water-based paint.
The coating method may be any method such as electrodeposition, spraying, dipping, rolling, and brushing. When the coating is performed by electrodeposition, the coating may be any of an anionic resin type and a cationic resin type.
【００１０】抗菌水溶液は、水に、銀又は銅を含む金属
塩を溶解し、還元剤を添加して作製する。好ましくは、
更にｐＨ７．５〜９．５の弱アルカリ性に調整して作製
する。金属塩としては、銀又は銅の、硫酸塩、硝酸塩、
塩化物、酢酸塩、シュウ酸塩、酒石酸塩等が用いられる
が、特にこれらに限るものではない。金属濃度は、０．
００１〜０．１％（重量％、以下同じ）とする。還元剤
としては、グルコース等の単糖類、サッカロース等の二
糖類、セルロース，デンプン，グリコーゲン等の多糖
類、エチレングリコール，プロピレングリコール，グリ
セリン等の多価アルコール、硫酸ヒドラジン，ヒドラジ
ンヒドラート等のヒドラジン類、水素化ホウ素ナトリウ
ム，水素化リチウム等の水素化物、次亜リン酸，次亜リ
ン酸ナトリウム等の次亜リン酸塩を用いることができ
る。抗菌水溶液は、イオン交換等によって硫酸根、硝酸
根等を除去して用いてもよい。この場合、錯形成剤とし
て、エチレンジアミン、エチレンジアミン四酢酸塩、ト
リエチレンテトラミン、ジエチレントリアミン、１，３
−ジアミノプロパン、ニトリロ三酢酸塩、アラニン、グ
リシン、ピコリン酸、ゼラチン等を、また、界面活性剤
として、アルキルベンゼンスルホン酸塩，アルキルエー
テル硫酸塩等のアニオン系界面活性剤、ポリオキシエチ
レンアルキルエーテル，ポリエチレングリコール等のノ
ニオン系界面活性剤を、用いることができる。弱アルカ
リ性への調整は、アミン類を添加して行う。アミン類と
しては、トリエチルアミン、トリエタノールアミン等を
用いることができる。The antibacterial aqueous solution is prepared by dissolving a metal salt containing silver or copper in water and adding a reducing agent. Preferably,
Further, it is prepared by adjusting the pH to a weak alkalinity of 7.5 to 9.5. As metal salts, silver or copper, sulfate, nitrate,
Chloride, acetate, oxalate, tartrate and the like are used, but not particularly limited thereto. The metal concentration is 0.
001 to 0.1% (% by weight, the same applies hereinafter). Examples of the reducing agent include monosaccharides such as glucose, disaccharides such as saccharose, polysaccharides such as cellulose, starch, and glycogen; polyhydric alcohols such as ethylene glycol, propylene glycol, and glycerin; hydrazines such as hydrazine sulfate and hydrazine hydrate. And hydrides such as sodium borohydride and lithium hydride, and hypophosphites such as hypophosphorous acid and sodium hypophosphite. The antibacterial aqueous solution may be used after removing sulfate groups, nitrate groups and the like by ion exchange or the like. In this case, ethylenediamine, ethylenediaminetetraacetate, triethylenetetramine, diethylenetriamine, 1,3
-Diaminopropane, nitrilotriacetate, alanine, glycine, picolinic acid, gelatin, etc .; A nonionic surfactant such as polyethylene glycol can be used. Adjustment to weak alkalinity is performed by adding amines. As the amines, triethylamine, triethanolamine and the like can be used.
【００１１】抗菌水溶液の塗膜表面への塗布は、スプレ
ー又は浸漬により行うのが好ましい。塗布量は、銀又は
銅として０．００００１〜０．１ｇ／ｍ2とするのが好
ましい。The application of the antibacterial aqueous solution to the surface of the coating film is preferably carried out by spraying or dipping. The coating amount is preferably 0.00001 to 0.1 g / m 2 as silver or copper.
【００１２】塗膜の焼成は、使用する塗料の標準焼成条
件でよい。一般には、６０〜３００℃で焼成する。The coating film may be fired under the standard firing conditions for the paint used. Generally, firing is performed at 60 to 300 ° C.
【００１３】本発明において、未焼成の塗膜の表面に抗
菌水溶液が塗布されると、抗菌水溶液中の銀イオン又は
銅イオンと還元剤とが塗膜表面から塗膜内部へ浸透して
いく。そして、塗膜が焼成されると、銀イオン又は銅イ
オンが還元されて銀又は銅の微粒子が生成する。銀イオ
ン又は銅イオンは塗膜内部へ円滑且つ確実に浸透してい
くので、銀又は銅の微粒子は、塗膜表面だけでなく、塗
膜内部にも多量に存在することとなる。従って、塗膜が
劣化して表面層が脱落しても、抗菌性は殆ど低下しな
い。In the present invention, when the antibacterial aqueous solution is applied to the surface of the unbaked coating film, silver ions or copper ions and the reducing agent in the antibacterial aqueous solution permeate from the coating film surface into the coating film. Then, when the coating film is fired, silver ions or copper ions are reduced to generate silver or copper fine particles. Since silver ions or copper ions smoothly and surely penetrate into the coating film, a large amount of silver or copper fine particles are present not only on the coating film surface but also inside the coating film. Therefore, even if the coating film deteriorates and the surface layer falls off, the antibacterial property hardly decreases.
【００１４】[0014]
【発明の実施の形態】（実施形態１） ・塗膜の形成 リン酸亜鉛処理した溶融亜鉛めっき鋼板を陰極として、
カチオン型アクリル樹脂系電着塗料（商品名「アクアN
o.４８３０ＬＡＩ」、日本油脂株式会社製）中で、５０
Ｖで３分間電解し、電着塗膜を形成した。この際の目標
膜厚は８μｍとした。 ・抗菌水溶液の作製 ０．０１％の銀を含む硫酸銀水溶液５００ｍｌに、Ｄ−
グルコース１．０ｇを加え、更に、トリエチルアミンを
添加してｐＨ８に調整して、抗菌水溶液を作製した。 ・処理 電着塗膜を、抗菌水溶液中に１分間浸漬した後、１７０
℃で３０分間焼成した。得られた電着塗膜中の銀量を分
析して求めたところ、０．００４ｇ／ｍ2であった。DESCRIPTION OF THE PREFERRED EMBODIMENTS (Embodiment 1)-Formation of coating film A hot-dip galvanized steel sheet treated with zinc phosphate is used as a cathode.
Cationic acrylic resin electrodeposition paint (trade name "Aqua N
o.4830 LAI ", manufactured by NOF Corporation
Electrolysis was performed at V for 3 minutes to form an electrodeposition coating film. The target film thickness at this time was 8 μm.・ Preparation of antibacterial aqueous solution In 500 ml of silver sulfate aqueous solution containing 0.01% silver, D-
1.0 g of glucose was added, and the pH was adjusted to 8 by further adding triethylamine to prepare an antibacterial aqueous solution.・ Treatment After immersing the electrodeposition coating film in the antibacterial aqueous solution for 1 minute,
Baking at 30 ° C. for 30 minutes. When the amount of silver in the obtained electrodeposition coating film was analyzed and determined, it was 0.004 g / m 2 .
【００１５】（実施形態２） ・塗膜の形成 純アルミニウム板（Ａ１１００Ｐ−Ｈ２４）を、常法に
より、脱脂処理、エッチング処理、及びスマット除去処
理した後、１７０ｇ／ｌ硫酸溶液中で陽極酸化処理し
て、厚さ１０μｍの陽極酸化皮膜を形成した。次に、こ
の陽極酸化皮膜を陽極として、アニオン型アクリル樹脂
系艶有り電着塗料（商品名「ハニーライトＡＬ−８００
Ｎ」、ハニー化成株式会社製）中で、１２０Ｖで３分間
電解し、電着塗膜を形成した。この際の目標膜厚は９μ
ｍとした。 ・抗菌水溶液の作製 ０．００５％の銀を含む硝酸銀水溶液５００ｍｌに、ニ
トリロトリ酢酸０．１ｇを加えた後、陰イオン交換樹脂
に通して硝酸根を除去した。次に、この水溶液に、エチ
レングリコール１ｍｌを加え、更に、トリエタノールア
ミンを添加してｐＨ８．５に調整して、抗菌水溶液を作
製した。 ・処理 電着塗膜に、塗装用スプレーガンを用いて抗菌水溶液を
塗布した後、１９０℃で３０分間焼成した。得られた電
着塗膜中の銀量を分析して求めたところ、０．００７ｇ
／ｍ2であった。(Embodiment 2) Formation of coating film A pure aluminum plate (A1100P-H24) is degreased, etched, and smut-removed by a conventional method, and then anodized in a 170 g / l sulfuric acid solution. As a result, an anodized film having a thickness of 10 μm was formed. Next, using this anodized film as an anode, an anionic acrylic resin-based glossy electrodeposition paint (trade name “Honeylight AL-800”)
N ", manufactured by Honey Chemical Co., Ltd.) at 120 V for 3 minutes to form an electrodeposition coating film. The target film thickness at this time is 9 μm.
m. Preparation of antibacterial aqueous solution 0.1 g of nitrilotriacetic acid was added to 500 ml of a silver nitrate aqueous solution containing 0.005% of silver, and then passed through an anion exchange resin to remove nitrate. Next, 1 ml of ethylene glycol was added to the aqueous solution, and triethanolamine was further added to adjust the pH to 8.5 to prepare an antibacterial aqueous solution. -Treatment An antibacterial aqueous solution was applied to the electrodeposited coating film using a spray gun for coating, and then baked at 190 ° C for 30 minutes. When the amount of silver in the obtained electrodeposition coating film was analyzed and determined, 0.007 g was obtained.
/ M 2 .
【００１６】（実施形態３） ・塗膜の形成 純チタン板を、３％リン酸と４％硫酸の混合溶液中で、
６０Ｖで５分間電解して、青色の干渉膜を形成した。次
に、この干渉膜に、ポリウレタン系塗料（商品名「アノ
ダールＳＰ−１リキッド」、クラリアント・ジャパン株
式会社製）をロール塗りし、厚さ２μｍの塗膜を形成し
た。 ・抗菌水溶液の作製 実施形態２と同じ抗菌水溶液を作製した。 ・処理 塗膜に、塗装用スプレーガンを用いて抗菌水溶液を塗布
した後、８０℃で２０分間焼成した。得られた電着塗膜
中の銀量を分析して求めたところ、０．００５ｇ／ｍ2
であった。(Embodiment 3) Formation of coating film A pure titanium plate is placed in a mixed solution of 3% phosphoric acid and 4% sulfuric acid.
Electrolysis was performed at 60 V for 5 minutes to form a blue interference film. Next, a polyurethane paint (trade name “Anodal SP-1 Liquid”, manufactured by Clariant Japan KK) was roll-coated on the interference film to form a coating film having a thickness of 2 μm. -Preparation of antibacterial aqueous solution The same antibacterial aqueous solution as in Embodiment 2 was prepared. -Treatment After the antibacterial aqueous solution was applied to the coating using a coating spray gun, the coating was baked at 80 ° C for 20 minutes. When the amount of silver in the obtained electrodeposition coating film was analyzed and determined, it was found to be 0.005 g / m 2.
Met.
【００１７】（実施形態４） ・塗膜の形成 アルミニウム合金板（Ａ６０６３Ｓ−Ｔ５）を、常法に
より、脱脂処理、エッチング処理、及びスマット除去処
理した後、陰極として、カチオン型アクリル樹脂系電着
塗料（商品名「アクアNo.４８３０ＬＡＩ」、日本油脂
株式会社製）中で、６０Ｖで３分間電解し、電着塗膜を
形成した。この際の目標膜厚は９μｍとした。 ・抗菌水溶液の作製 ０．０５％の銅を含む酢酸銅水溶液５００ｍｌに、ヒド
ラジンヒドラート１．０ｍｌを加えて作製した。なお、
ｐＨは９．１であった。 ・処理 電着塗膜を、抗菌水溶液中に３分間浸漬した後、１７０
℃で３０分間焼成した。得られた電着塗膜中の銅量を分
析して求めたところ、０．０１２ｇ／ｍ2であった。(Embodiment 4)-Formation of coating film Aluminum alloy plate (A6063S-T5) is subjected to degreasing, etching, and smut removal by a conventional method, and then a cationic acrylic resin electrodeposition is used as a cathode. Electrolysis was performed at 60 V for 3 minutes in a paint (trade name “Aqua No. 4830 LAI”, manufactured by NOF CORPORATION) to form an electrodeposition coating film. The target film thickness at this time was 9 μm. Preparation of Antibacterial Aqueous Solution To 500 ml of an aqueous copper acetate solution containing 0.05% of copper, 1.0 ml of hydrazine hydrate was added. In addition,
pH was 9.1.・ Treatment After immersing the electrodeposition coating film in the antibacterial aqueous solution for 3 minutes,
Baking at 30 ° C. for 30 minutes. It was 0.012 g / m < 2 > when the amount of copper in the obtained electrodeposition coating film was analyzed and calculated | required.
【００１８】（比較形態１）抗菌水溶液への浸漬を行わ
ない点以外は、実施形態１と同様に行った。(Comparative Embodiment 1) The same procedure as in Embodiment 1 was performed except that the immersion in the antibacterial aqueous solution was not performed.
【００１９】（比較形態２）抗菌水溶液の塗布を行わな
い点以外は、実施形態２と同様に行った。(Comparative Embodiment 2) The same operation as in Embodiment 2 was performed except that the application of the antibacterial aqueous solution was not performed.
【００２０】（比較形態３）抗菌水溶液の塗布を行わな
い点以外は、実施形態３と同様に行った。Comparative Example 3 The same procedure as in Example 3 was carried out except that the application of the antibacterial aqueous solution was not performed.
【００２１】（比較形態４）抗菌水溶液への浸漬を行わ
ない点以外は、実施形態４と同様に行った。(Comparative Embodiment 4) The same procedure as in Embodiment 4 was carried out except that immersion in the antibacterial aqueous solution was not performed.
【００２２】（試験）実施形態１〜４及び比較形態１〜
４で得た塗膜について、その抗菌性を、銀等無機抗菌剤
研究会制定のフィルム密着法に準拠して、評価した。フ
ィルム密着法とは、５０×５０ｍｍの平板状の試験片
に、１／５００普通ブイヨン培地に１×１０5ｃｆｕの
菌を均一に分散させてなる接種用菌液０．５ｍｌを接種
し、その上に同じ形状のポリエチレン製フィルムを載
せ、これを３５℃で２４時間培養し、その後、生存菌数
を寒天平板法により測定する方法である。なお、ここで
は、菌として、大腸菌及び黄色ブトウ球菌を用いた。表
１に、各塗膜試験片の抗菌性の評価結果を示す。(Test) Embodiments 1-4 and Comparative Embodiments 1
The antibacterial property of the coating film obtained in No. 4 was evaluated in accordance with the film adhesion method established by the Study Group for Inorganic Antibacterial Agents such as Silver. The film adhesion method is to inoculate 0.5 ml of a bacterial solution for inoculation prepared by uniformly dispersing 1 × 10 5 cfu of bacteria in a 1/500 ordinary broth medium on a 50 × 50 mm plate-shaped test piece. This is a method in which a polyethylene film of the same shape is placed on the top, cultured at 35 ° C. for 24 hours, and then the number of viable bacteria is measured by an agar plate method. Here, Escherichia coli and Staphylococcus aureus were used as bacteria. Table 1 shows the evaluation results of the antibacterial properties of each coating film test piece.
【００２３】[0023]
【表１】 [Table 1]
【００２４】表１から明らかなように、実施形態１〜４
の塗膜では、いずれも生存菌数が１００未満即ち検出限
界以下であり、優れた抗菌性が発揮されているが、比較
形態１〜４の塗膜では、いずれも多くの菌が残存してお
り、抗菌性は見られなかった。As is clear from Table 1, Embodiments 1 to 4
In the coating film, the number of surviving bacteria is less than 100, that is, below the detection limit, and excellent antibacterial properties are exhibited, but in the coating films of Comparative Examples 1 to 4, many bacteria remain. And no antibacterial properties were observed.
【００２５】[0025]
【発明の効果】以上のように、本発明によれば、塗膜表
面だけでなく、塗膜内部にも、銀又は銅の微粒子を多量
に存在させることができるので、十分な抗菌性を発揮で
きる塗膜を得ることができる。As described above, according to the present invention, a large amount of silver or copper fine particles can be present not only on the surface of the coating film but also inside the coating film, so that sufficient antibacterial properties are exhibited. The resulting coating film can be obtained.
Claims (1)
いて、 未焼成の塗膜の表面に、銀イオン又は銅イオンと還元剤
とを含んでなる抗菌水溶液を塗布し、その後、塗膜を焼
成して銀イオン又は銅イオンを還元することを特徴とす
る抗菌塗膜の製造方法。1. A method for producing a coating film having antibacterial properties, comprising: applying an antibacterial aqueous solution containing silver ions or copper ions and a reducing agent to the surface of an unfired coating film; A method for producing an antibacterial coating film, comprising reducing silver ions or copper ions by baking.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10753898A JPH11302570A (en) | 1998-04-17 | 1998-04-17 | Production of antimicrobial coating film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10753898A JPH11302570A (en) | 1998-04-17 | 1998-04-17 | Production of antimicrobial coating film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH11302570A true JPH11302570A (en) | 1999-11-02 |
Family
ID=14461739
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10753898A Pending JPH11302570A (en) | 1998-04-17 | 1998-04-17 | Production of antimicrobial coating film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH11302570A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006282629A (en) * | 2005-04-04 | 2006-10-19 | Taiko:Kk | Spray composition |
| GB2449893A (en) * | 2007-06-07 | 2008-12-10 | Aguacure Ltd | Antimicrobial composition |
| US8309216B2 (en) | 2006-04-07 | 2012-11-13 | Bactiguard Ab | Substrate having an electron donating surface with metal particles comprising palladium on said surface |
| US8858775B2 (en) | 2007-10-03 | 2014-10-14 | Accentus Medical Limited | Method of manufacturing metal with biocidal properties |
| US8945363B2 (en) | 2002-04-16 | 2015-02-03 | Accentus Medical Limited | Method of making metal implants |
| US9011665B2 (en) | 2004-03-13 | 2015-04-21 | Accentus Medical Limited | Metal implants |
-
1998
- 1998-04-17 JP JP10753898A patent/JPH11302570A/en active Pending
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8945363B2 (en) | 2002-04-16 | 2015-02-03 | Accentus Medical Limited | Method of making metal implants |
| US9393349B2 (en) | 2002-04-16 | 2016-07-19 | Accentus Medical Limited | Metal implants |
| US9011665B2 (en) | 2004-03-13 | 2015-04-21 | Accentus Medical Limited | Metal implants |
| JP2006282629A (en) * | 2005-04-04 | 2006-10-19 | Taiko:Kk | Spray composition |
| US8309216B2 (en) | 2006-04-07 | 2012-11-13 | Bactiguard Ab | Substrate having an electron donating surface with metal particles comprising palladium on said surface |
| US8394494B2 (en) | 2006-04-07 | 2013-03-12 | Bactiguard Ab | Antimicrobial substrates and uses thereof |
| US8470453B2 (en) | 2006-04-07 | 2013-06-25 | Bactiguard Ab | Biocompatible substrates and uses thereof |
| US8765256B2 (en) | 2006-04-07 | 2014-07-01 | Bactiguard Ab | Substrate having an electron donating surface with metal particles comprising palladium on said surface |
| US9339588B2 (en) | 2006-04-07 | 2016-05-17 | Bactiguard Ab | Substrate having an electron donating surface with metal particles comprising palladium on said surface |
| US9872942B2 (en) | 2006-04-07 | 2018-01-23 | Bactigaurd AB | Substrate having an electron donating surface with metal particles comprising palladium on said surface |
| GB2449893A (en) * | 2007-06-07 | 2008-12-10 | Aguacure Ltd | Antimicrobial composition |
| US8858775B2 (en) | 2007-10-03 | 2014-10-14 | Accentus Medical Limited | Method of manufacturing metal with biocidal properties |
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