JP2002187806A - Antimicrobial material - Google Patents
Antimicrobial materialInfo
- Publication number
- JP2002187806A JP2002187806A JP2000387085A JP2000387085A JP2002187806A JP 2002187806 A JP2002187806 A JP 2002187806A JP 2000387085 A JP2000387085 A JP 2000387085A JP 2000387085 A JP2000387085 A JP 2000387085A JP 2002187806 A JP2002187806 A JP 2002187806A
- Authority
- JP
- Japan
- Prior art keywords
- titanium dioxide
- silver
- film
- antibacterial
- substrate
- 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、二酸化チタン系抗
菌性材料に関する。[0001] The present invention relates to a titanium dioxide antibacterial material.
【０００２】[0002]
【従来の技術】二酸化チタンは、紫外線により光活性を
示すことが知られ、この光活性による光触媒作用を利用
した有機物質の分解が行われている。この際、光活性に
優れたアナターゼ型二酸化チタン膜を効率良く基材上に
形成する必要があった。2. Description of the Related Art Titanium dioxide is known to exhibit photoactivity by ultraviolet rays, and organic substances are decomposed by utilizing photocatalysis by this photoactivity. At this time, it was necessary to efficiently form an anatase type titanium dioxide film having excellent photoactivity on the substrate.
【０００３】従来、上記二酸化チタン膜を基材上に形成
する方法としては、塗布や下記の種々の方法が行われて
いるが、そのいずれもが下記の通りの多くの問題があ
る。すなわち、塗布の場合は、アナターゼ型二酸化チタ
ン微粒子をバインダーに分散させて行うために、全表面
に占める二酸化チタンの比率が少なく、光触媒効果は十
分でない。Conventionally, as a method of forming the above-mentioned titanium dioxide film on a substrate, coating and various methods described below have been performed, but all of them have many problems as described below. That is, in the case of coating, since the anatase type titanium dioxide fine particles are dispersed in a binder, the ratio of titanium dioxide to the entire surface is small, and the photocatalytic effect is not sufficient.
【０００４】基材表面に直接二酸化チタン膜を形成させ
る方法としては、チタン鋼表面の酸化や金属基材上への
二酸化チタン溶射等があるが、いずれも基材が限定され
ており、それらの光触媒効果も十分でない。又、金属基
材や一部プラスチック基材の場合には、複合メッキの技
術を用い、湿式の電解或いは無電解メッキの際、メッキ
液中にアナターゼ型二酸化チタン微粒子を分散させるこ
とにより二酸化チタンを含むメッキ膜を形成させること
が可能であるが、基材表面における二酸化チタンの比率
が低いため光活性は十分でない。As a method of forming a titanium dioxide film directly on the surface of a base material, there are oxidation of the surface of titanium steel and spraying of titanium dioxide on a metal base material. The photocatalytic effect is not enough. In addition, in the case of a metal substrate or a partly plastic substrate, titanium dioxide is dispersed by dispersing anatase type titanium dioxide fine particles in a plating solution at the time of wet electrolysis or electroless plating using a composite plating technique. Although it is possible to form a plating film containing the same, the photoactivity is not sufficient because the ratio of titanium dioxide on the substrate surface is low.
【０００５】このような低い光活性のため、蛍光灯等に
よる紫外線照射では、光触媒効果が不十分であったり、
光触媒として機能させるためブラックライト等の紫外線
発生源を極く間近かに設置させる必要があった。[0005] Due to such low photoactivity, the photocatalytic effect is insufficient by ultraviolet irradiation with a fluorescent lamp or the like,
In order to function as a photocatalyst, an ultraviolet light source such as a black light had to be placed very close.
【０００６】又、二酸化チタン等の金属酸化物、硫化カ
ドミウム等の金属硫化物、セレン化カドミウム等の金属
セレン化物、リン酸ゲルマニム等の金属リン化物等、或
いはこれらに白金、ロジウム、ルテニウム、鉄又は銅を
担持したものを基材上にＰＶＤ法で成膜することも試み
られているが（特開平９−１９２４９８号公報）、これ
らの内二酸化チタンが触媒活性その他が高く特に好まし
いとしている。Further, metal oxides such as titanium dioxide, metal sulfides such as cadmium sulfide, metal selenides such as cadmium selenide, metal phosphides such as germanium phosphate, or platinum, rhodium, ruthenium, iron Alternatively, an attempt has been made to form a film supporting copper on a substrate by a PVD method (Japanese Patent Application Laid-Open No. 9-192498), and among these, titanium dioxide is considered to be particularly preferable because of its high catalytic activity and the like.
【０００７】更に、二酸化チタンの光触媒作用として抗
菌作用を示すことが知られているが、光照射時間を長く
するか照射強度を大きくしないとその作用効果は認めら
れず、光照射がないと抗菌作用を全く示さない。Further, it is known that titanium dioxide exhibits an antibacterial action as a photocatalytic action. However, the effect cannot be recognized unless the light irradiation time is increased or the irradiation intensity is increased. Shows no effect.
【０００８】一方、銀（金属、イオン、酸化物）は抗菌
性を有することが知られており、素材そのものを銀にす
るか、これを成分とする抗菌剤が開発され実用されてい
る。従来、これを成分とする抗菌剤は、銀の微粉末やそ
れを無機質担体に担持したもの等を、基材内部に含有さ
せたり、基材表面に沈着させたり、基材表面に塗布した
りするか、或いは銀金属を基材表面にメッキする等の方
法が採用されている。[0008] On the other hand, silver (metal, ion, oxide) is known to have antibacterial properties, and an antibacterial agent made of silver itself or containing it as a component has been developed and put to practical use. Conventionally, as an antibacterial agent containing this as a component, a fine silver powder or a powder obtained by supporting the same on an inorganic carrier is contained in a base material, deposited on a base material surface, or applied to a base material surface. Or a method of plating silver metal on the surface of the base material.
【０００９】しかし、上記抗菌成分を基材内部に含有さ
せたものは大量に抗菌成分を基材内部に含有させない
と、抗菌作用が低く、用いられる基材も限られる。又、
上記抗菌成分を基材表面に沈着又は塗布させたものは基
材表面との密着性に劣ることから、耐久性に問題があ
り、基材表面に銀メッキしたものは、基材表面全体に銀
メッキする必要があり、高価な銀を多量に必要とすると
共に基材表面との密着性に劣り、耐久性に問題がある。However, the antibacterial component contained in the base material has a low antibacterial effect unless the antibacterial component is contained in a large amount in the base material, and the base material used is limited. or,
Those having the antimicrobial component deposited or coated on the substrate surface have poor durability because of poor adhesion to the substrate surface, and those having silver plating on the substrate surface have silver on the entire substrate surface. It requires plating, which requires a large amount of expensive silver, has poor adhesion to the substrate surface, and has a problem in durability.
【００１０】[0010]
【発明が解決しようとする課題】本発明は、光照射の有
無に関係なく大きな抗菌作用を示し、基材表面との密着
性が良好で耐久性に優れ、安価な二酸化チタン系抗菌性
材料を提供することを目的とする。SUMMARY OF THE INVENTION The present invention provides a low-cost titanium dioxide antibacterial material which exhibits a large antibacterial action regardless of the presence or absence of light irradiation, has good adhesion to the substrate surface, has excellent durability, and is inexpensive. The purpose is to provide.
【００１１】[0011]
【課題を解決するための手段】本発明者らは、上記の問
題点を改善すべく鋭意検討した結果、二酸化チタンに銀
を組み合わせて基材上に真空蒸着法により皮膜を形成し
た材料が、本発明の目的を達成し得ることを見出し、本
発明に到達した。Means for Solving the Problems The inventors of the present invention have conducted intensive studies to improve the above-mentioned problems, and as a result, a material obtained by forming a film on a substrate by combining titanium dioxide and silver by a vacuum evaporation method has been proposed. The inventors have found that the object of the present invention can be achieved, and have reached the present invention.
【００１２】すなわち、本発明は、基材の表面に二酸化
チタン及び銀からなる皮膜を真空蒸着法により形成して
なる抗菌性材料を要旨とする。又、本発明の抗菌性材料
は、上記皮膜中の銀の含有量が１．０〜７０質量％であ
ることを特徴とする。又、本発明の抗菌性材料は、上記
真空蒸着法がイオンプレーティング法により二酸化チタ
ン及び銀を蒸発させながら同時に成膜させることを特徴
とする。That is, the gist of the present invention is an antibacterial material obtained by forming a film made of titanium dioxide and silver on a surface of a substrate by a vacuum deposition method. Further, the antibacterial material of the present invention is characterized in that the content of silver in the film is 1.0 to 70% by mass. Further, the antibacterial material of the present invention is characterized in that the above-mentioned vacuum vapor deposition method simultaneously forms a film while evaporating titanium dioxide and silver by an ion plating method.
【００１３】[0013]
【発明の実施の形態】本発明で用いられる二酸化チタン
は、耐蝕処理用として真空蒸着法で用いられている汎用
のルチル型二酸化チタンが好適であるが、アナターゼ
型、ブルッカイト型、更には非晶質の二酸化チタンでも
良い。なぜならば、るつぼに入れられた二酸化チタン原
料はいったん蒸発し、基材上に蒸着するため、初期の結
晶構造は蒸着膜の結晶に直接影響を与えないからであ
る。BEST MODE FOR CARRYING OUT THE INVENTION The titanium dioxide used in the present invention is preferably a general-purpose rutile type titanium dioxide used in a vacuum deposition method for corrosion resistance treatment, but is preferably an anatase type, a brookite type, or an amorphous type. High quality titanium dioxide may be used. This is because the titanium dioxide raw material put in the crucible evaporates once and is deposited on the base material, so that the initial crystal structure does not directly affect the crystal of the deposited film.
【００１４】本発明で用いられる成膜方法は真空蒸着法
であるが、成膜の密着性等を考慮すると、イオンプレー
ティング法により二酸化チタン及び銀を蒸発させながら
同時に基材上に成膜させる方法が特に好ましい。原料の
蒸発方法としては、多陰極熱電子照射法、中空陰極法、
熱陰極法、アークプラズマ法等既存の技術を採用するこ
とができる。The film forming method used in the present invention is a vacuum deposition method. However, in consideration of the adhesion of the film, the film is formed on the substrate at the same time as titanium dioxide and silver are evaporated by ion plating. The method is particularly preferred. As a method for evaporating the raw materials, a multi-cathode thermionic irradiation method, a hollow cathode method,
Existing technologies such as a hot cathode method and an arc plasma method can be employed.
【００１５】基材としては、真空蒸着法、特にイオンプ
レーティング条件下、材料からのガス放出、材料の変形
等がなければ、どのような材料を用いることができ、合
金を含む各種金属材料、ガラスやセラミック等の無機材
料、プラスチック等が使用可能である。As the substrate, any material can be used as long as there is no outgassing from the material, no deformation of the material, etc. under the vacuum deposition method, especially under the condition of ion plating, and various metal materials including alloys, Inorganic materials such as glass and ceramics, plastics and the like can be used.
【００１６】基材上に成膜される二酸化チタンと銀の複
合皮膜の厚さは、１００オングストローム（１０ｎｍ）
〜５０μｍであり、皮膜の密着性や強度等を考慮すれ
ば、０．１〜１０μｍが好ましい。The thickness of the composite film of titanium dioxide and silver formed on the substrate is 100 angstroms (10 nm).
To 50 μm, and preferably 0.1 to 10 μm in consideration of the adhesion and strength of the film.
【００１７】複合皮膜はその中に、１．０〜７０質量％
の銀を含むのが好ましく、皮膜物性を考慮すると、銀の
含有量は特に好ましくは５．０〜５０質量％である。銀
の含有量が１．０質量％未満では、銀を複合した効果が
得られず、７０質量％を超えると、皮膜の強度が低下し
てしまい、望ましくはない。The composite coating contains 1.0 to 70% by mass
Is preferable, and in consideration of the film properties, the silver content is particularly preferably 5.0 to 50% by mass. If the silver content is less than 1.0% by mass, the effect of combining silver cannot be obtained, and if it exceeds 70% by mass, the strength of the coating film is undesirably reduced.
【００１８】金属酸化物の真空蒸着では、得られる皮膜
の組成式が整数にならず、そのため真空中に酸素ガスを
導入し、ある程度の酸素分圧下で蒸着されることもある
が、本発明においても同様の手法を用いることには何ら
問題がない。In the vacuum deposition of metal oxide, the composition formula of the obtained film is not an integer. For this reason, an oxygen gas may be introduced into a vacuum and the film may be deposited under a certain oxygen partial pressure. There is no problem using the same method.
【００１９】上記のようにして得られる複合皮膜は、Ｘ
線回折にて二酸化チタンの結晶形であるルチル型やアナ
ターゼ型特有の回折を示さず、二酸化チタンはアモルフ
ァス（非晶質）である。The composite film obtained as described above has X
The line diffraction does not show diffraction unique to the rutile type or anatase type which are crystal forms of titanium dioxide, and titanium dioxide is amorphous.
【００２０】上記本発明の光触媒材料は、その形状は何
ら決められるものではなく、フィルム状、シート状、板
状、ブロック状、円柱状等、使用される用途に応じて任
意に加工することができる。The shape of the photocatalyst material of the present invention is not limited at all, and can be arbitrarily processed according to the intended use, such as a film, a sheet, a plate, a block, and a column. it can.
【００２１】[0021]
【実施例】以下、本発明を実施例により、詳細に説明す
る。 （実施例）ルチル型二酸化チタンと銀を原料として、５
０ｍｍ×５０ｍｍ×１．０ｍｍのＳＵＳ３０４製板の片
面上に、複合皮膜中の銀の含有量が１、５、１０又は３
０質量％になるように厚さ１．０μｍの二酸化チタン・
銀の複合皮膜をイオンプレーティング法により形成し
た。The present invention will be described below in detail with reference to examples. (Example) Using rutile-type titanium dioxide and silver as raw materials, 5
On one side of a SUS304 plate of 0 mm × 50 mm × 1.0 mm, the silver content in the composite coating was 1, 5, 10 or 3
1.0 μm thick titanium dioxide
A silver composite film was formed by an ion plating method.
【００２２】（比較例１）ルチル型二酸化チタンと銀か
らなる原料の代りに、ルチル型二酸化チタンからなる原
料、又は銀からなる原料を用いた以外は、実施例と同様
にして厚さ１．０μｍの二酸化チタンの単独皮膜及び銀
の単独皮膜をイオンプレーティング法により形成した。Comparative Example 1 The procedure of Example 1 was repeated except that a raw material made of rutile titanium dioxide or a raw material made of silver was used instead of the raw material made of rutile titanium dioxide and silver. A single layer of 0 μm titanium dioxide and a single layer of silver were formed by ion plating.
【００２３】抗菌効果の確認試験 指標菌としてＥ．coliＩＡＭ12119 を用いた。水酸化ナ
トリウムでｐＨ７．０に調整したリン緩衝液に、対数期
にあるＥ．coliＩＡＭ12119 を懸濁させ、Ｅ．coliＩＡ
Ｍ12119 をおよそ１０4 ／ｃｍ3 個〜１０5 ／ｃｍ3 個
含む菌液を調整した。実施例及び比較例１で作製した各
種試料並びに何ら処理しないＳＵＳ３０４製板（未処理
板）を、滅菌シャーレーに置き、その中央部に菌液を
０．５ｍｌ滴下して試料と菌液を所定時間接触させた。
上記菌液と接触させた試料について、紫外線照射するか
しないで抗菌効果を調べたが、紫外線照射する場合は、
上記菌液と接触させると同時に、波長３６０ｎｍ付近に
分布のピークがある紫外線ランプを用いて、上記各試料
の表面における強度が２０〜３５μＷ／ｃｍ2 になるよ
うに、紫外線を照射しながら室温で所定時間放置した。
紫外線照射しない場合は、そのまま菌液と接触させなが
ら室温で所定時間放置した。所定時間経過後、リン緩衝
液を用いて試料表面から菌液を洗い落とし、適量を採り
標準寒天培地にて混釈し、３７℃で２４時間培養後のコ
ロニー数を計数した。それらの結果を表１に示した。 Confirmation test of antibacterial effect coli IAM12119 was used. Phosphorus buffer adjusted to pH 7.0 with sodium hydroxide was added to E. coli in the log phase. E. coli IAM12119 was suspended in E. coli. coli IA
A bacterial solution containing approximately 10 4 / cm 3 to 10 5 / cm 3 of M12119 was prepared. Various samples prepared in Examples and Comparative Example 1 and a SUS304 plate (untreated plate) not subjected to any treatment were placed in a sterile petri dish, and 0.5 ml of a bacterial solution was dropped on the center of the plate, and the sample and the bacterial solution were allowed to stand for a predetermined time. Contacted.
The antimicrobial effect of the sample contacted with the bacterial solution was examined with or without UV irradiation.
At the same time as contacting with the bacterial solution, using an ultraviolet lamp having a distribution peak near a wavelength of 360 nm, at room temperature while irradiating with ultraviolet rays such that the intensity on the surface of each sample becomes 20 to 35 μW / cm 2. It was left for a predetermined time.
In the case where ultraviolet irradiation was not performed, the sample was left at room temperature for a predetermined time while being kept in contact with the bacterial solution. After a lapse of a predetermined time, the bacterial solution was washed off from the surface of the sample using a phosphorus buffer, and an appropriate amount was taken out, mixed with a standard agar medium, and the number of colonies after culturing at 37 ° C for 24 hours was counted. The results are shown in Table 1.
【００２４】[0024]
【表１】 [Table 1]
【００２５】表１から明らかのように、未処理板からな
る試料では、接触時間を長くし、かつ紫外線照射しても
菌数に変化がなく、二酸化チタン単独皮膜からなる試料
では、紫外線照射しても、接触時間を長くしないと菌数
は減少しなく、又、銀単独皮膜からなる試料では、紫外
線照射しても、或る程度接触時間を長くしないと菌数は
１０未満にはならないことが判る。As is clear from Table 1, the contact time of the sample made of an untreated plate was prolonged, and the number of bacteria did not change even when the sample was irradiated with ultraviolet rays. However, the number of bacteria does not decrease unless the contact time is increased, and in the case of a sample consisting of a silver-only film, the number of bacteria does not become less than 10 unless the contact time is extended to some extent, even when irradiated with ultraviolet light. I understand.
【００２６】これに対して、実施例で作製した二酸化チ
タン・銀の複合皮膜からなる試料では、紫外線照射する
と菌数は大幅に減少し、特に銀の含有量が５質量％以上
になると接触時間が３時間でも菌数が１０未満に減少
し、これは銀単独皮膜からなる試料の接触時間が５時間
のものと同等である。これは二酸化チタンと銀を併用し
た相乗作用のためであると考えられる。On the other hand, in the sample made of the composite film of titanium dioxide / silver prepared in the examples, the number of bacteria is greatly reduced by ultraviolet irradiation, and especially when the silver content becomes 5% by mass or more, the contact time becomes shorter. The number of bacteria decreased to less than 10 even after 3 hours, which is equivalent to the case where the contact time of the sample consisting of the silver-only film was 5 hours. This is thought to be due to the synergistic effect of using titanium dioxide and silver in combination.
【００２７】又、銀は抗菌作用があるため紫外線の照射
がなくても抗菌性を示すが、二酸化チタン・銀の複合皮
膜からなる試料も同等の抗菌性を示すことが表１の結果
から判断される。以上から、二酸化チタン・銀の複合皮
膜からなる試料は、紫外線のない環境と同等の、そして
紫外線照射下ではそれ以上の優れた抗菌性を示すことが
判明した。Since silver has an antibacterial effect, it exhibits antibacterial properties even without irradiation with ultraviolet rays, but it can be judged from the results in Table 1 that the sample composed of a composite film of titanium dioxide and silver exhibits the same antibacterial properties. Is done. From the above, it was found that the sample composed of the titanium dioxide / silver composite film exhibited excellent antibacterial properties equivalent to those in an environment without ultraviolet rays, and more excellent under ultraviolet irradiation.
【００２８】（比較例２）ルチル型二酸化チタンと銀か
らなる原料の代りに、ルチル型二酸化チタンとパラジウ
ム又は白金からなる原料を、成膜後のパラジウム又は白
金の含有量がそれぞれ１０質量％になるようにして用い
た以外は、実施例と同様にして厚さ１．０μｍの二酸化
チタン・パラジウム又は二酸化チタン・白金の複合皮膜
をイオンプレーティング法により形成した。得られた各
試料について、上記と同様にして抗菌効果の確認試験を
行い、それらの結果を表２に示した。又、実施例と同様
にして得た二酸化チタン・銀の複合皮膜からなる試料に
ついてついても、同様にして抗菌効果の確認試験を行
い、それらの結果を表２に示した。(Comparative Example 2) Instead of the raw material consisting of rutile-type titanium dioxide and silver, the raw material consisting of rutile-type titanium dioxide and palladium or platinum was replaced with a palladium or platinum content of 10% by mass after film formation. A composite film of titanium dioxide / palladium or titanium dioxide / platinum having a thickness of 1.0 μm was formed by an ion plating method in the same manner as in the example except that it was used as described above. For each of the obtained samples, a confirmation test of the antibacterial effect was performed in the same manner as described above, and the results are shown in Table 2. In addition, with respect to a sample comprising a composite film of titanium dioxide and silver obtained in the same manner as in the example, a test for confirming the antibacterial effect was carried out in the same manner, and the results are shown in Table 2.
【００２９】[0029]
【表２】 [Table 2]
【００３０】表２から明らかのように、比較例２で作製
した複合皮膜からなる試料は、紫外線を照射しないと抗
菌性を示さないことが判明した。As is evident from Table 2, it was found that the sample comprising the composite film prepared in Comparative Example 2 did not exhibit antibacterial properties unless irradiated with ultraviolet rays.
【００３１】[0031]
【発明の効果】本発明の抗菌性材料は、高価な銀を二酸
化チタンに対して数質量％程度含有させることにより、
抗菌剤として一般に用いられている銀と同等か、それ以
上の抗菌性を示す。従って、安価な抗菌性材料を提供す
ることができ、基材表面との密着性に優れることから寿
命が長いという利点を有している。The antibacterial material of the present invention contains expensive silver in an amount of about several mass% with respect to titanium dioxide.
Shows antibacterial properties equal to or better than silver generally used as an antibacterial agent. Therefore, it is possible to provide an inexpensive antibacterial material, and has an advantage that it has a long life due to its excellent adhesion to the substrate surface.
【００３２】又、本発明の抗菌性材料は、金属類、セラ
ミック類、ガラス、プラスチック等多くの材料を基材と
して用いることができ、抗菌作用が極めて優れているた
めに、清潔性が要求される食料品分野、医薬・医療分
野、飲料分野、業務用・家庭用調理製品分野、浴室分
野、トイレ分野等の他、家庭用雑貨品、玩具、各種成形
材等多種多様な分野に利用することができる。The antibacterial material of the present invention can use many materials such as metals, ceramics, glass, and plastics as a base material, and is required to be clean because of its extremely excellent antibacterial action. Be used in a wide variety of fields such as foodstuffs, medicine / medical care, beverages, commercial / home cooking products, bathrooms, toilets, etc., as well as household goods, toys, and various molding materials. Can be.
Claims (3)
る皮膜を真空蒸着法により形成してなる抗菌性材料。1. An antibacterial material comprising a film made of titanium dioxide and silver formed on a surface of a substrate by a vacuum deposition method.
質量％であることを特徴とする請求項１記載の抗菌性材
料。2. The silver content in the coating is 1.0 to 70.
The antibacterial material according to claim 1, wherein the content is mass%.
法により二酸化チタン及び銀を蒸発させながら同時に成
膜させることを特徴とする請求項１又は２記載の抗菌性
材料。3. The antibacterial material according to claim 1, wherein the vacuum deposition method comprises simultaneously forming a film while evaporating titanium dioxide and silver by an ion plating method.
Priority Applications (1)
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|---|---|---|---|
| JP2000387085A JP2002187806A (en) | 2000-12-20 | 2000-12-20 | Antimicrobial material |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000387085A JP2002187806A (en) | 2000-12-20 | 2000-12-20 | Antimicrobial material |
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| Publication Number | Publication Date |
|---|---|
| JP2002187806A true JP2002187806A (en) | 2002-07-05 |
Family
ID=18854079
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000387085A Pending JP2002187806A (en) | 2000-12-20 | 2000-12-20 | Antimicrobial material |
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| Country | Link |
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| JP2002186860A (en) * | 2000-12-20 | 2002-07-02 | Nihon Tetra Pak Kk | Photocatalyst material |
| FR2887560A1 (en) * | 2005-06-28 | 2006-12-29 | Commissariat Energie Atomique | COMPOSITE METAL AND OXIDE FILMS FOR ANTIMICROBIAL APPLICATIONS AND METHOD FOR PROTECTING OR DECONTAMINATING A SUBSTRATE USING SUCH FILMS |
| CN100382705C (en) * | 2003-06-10 | 2008-04-23 | 香港理工大学 | Multifunctional broad spectrum nanometer antibiotic material and its preparation method |
| EP1933079A1 (en) * | 2006-12-14 | 2008-06-18 | AGC Flat Glass Europe SA | Illuminated panel |
| WO2010024598A2 (en) * | 2008-08-27 | 2010-03-04 | 주식회사 지피엔이 | Method for preparing antimicrobial, antifungal, and antiviral compositions |
| WO2015040558A1 (en) * | 2013-09-17 | 2015-03-26 | Theta Chemicals Limited | A dual action antimicrobial film |
| CN113106399A (en) * | 2020-12-29 | 2021-07-13 | 阳江市新辉科技有限公司 | Multicolor antibacterial film layer and preparation method and application thereof |
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