JPWO2009110233A1 - 抗菌性材料とそれを用いた抗菌性膜および抗菌性部材 - Google Patents
抗菌性材料とそれを用いた抗菌性膜および抗菌性部材 Download PDFInfo
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- JPWO2009110233A1 JPWO2009110233A1 JP2010501800A JP2010501800A JPWO2009110233A1 JP WO2009110233 A1 JPWO2009110233 A1 JP WO2009110233A1 JP 2010501800 A JP2010501800 A JP 2010501800A JP 2010501800 A JP2010501800 A JP 2010501800A JP WO2009110233 A1 JPWO2009110233 A1 JP WO2009110233A1
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- Prior art keywords
- antibacterial
- fine particles
- tungsten oxide
- tungsten
- powder
- 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.)
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- 239000000463 material Substances 0.000 title claims abstract description 102
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- RJQXTJLFIWVMTO-TYNCELHUSA-N Methicillin Chemical compound COC1=CC=CC(OC)=C1C(=O)N[C@@H]1C(=O)N2[C@@H](C(O)=O)C(C)(C)S[C@@H]21 RJQXTJLFIWVMTO-TYNCELHUSA-N 0.000 claims abstract description 10
- 241000589517 Pseudomonas aeruginosa Species 0.000 claims abstract description 10
- 229960003085 meticillin Drugs 0.000 claims abstract description 10
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Classifications
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
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- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2/00—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor
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- A61L2/00—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor
- A61L2/16—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor using chemical substances
- A61L2/23—Solid substances, e.g. granules, powders, blocks, tablets
- A61L2/238—Metals or alloys, e.g. oligodynamic metals
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- A—HUMAN NECESSITIES
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- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L9/00—Disinfection, sterilisation or deodorisation of air
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- A—HUMAN NECESSITIES
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- A61L9/00—Disinfection, sterilisation or deodorisation of air
- A61L9/01—Deodorant compositions
- A61L9/014—Deodorant compositions containing sorbent material, e.g. activated carbon
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Abstract
Description
R=log(B1/C1)
(式中、B1は無加工試験片を24時間保存した後の生菌数の平均値(個)、C1は前記微粒子を塗布した前記試験片を24時間保存した後の生菌数の平均値(個)である)
で表される抗菌活性値Rが0.1以上であることを特徴としている。
R=log(B1/C1) …(1)
RD=log(BD/CD) …(2)
RL=log(BL/CL) …(3)
タングステン酸アニモニウム塩を大気中にて900℃で2時間加熱した後、ボールミルで粉砕することによって、酸化タングステン微粒子を作製した。得られた酸化タングステン微粒子の平均一次粒子径(D50)とBET比表面積を測定した。平均一次粒子径はTEM写真の画像解析によって測定した。TEM観察には日立社製H−7100FAを使用し、拡大写真を画像解析にかけて粒子50個以上を抽出し、体積基準の積算径を求めてD50を算出した。BET比表面積の測定は、マウンテック社製比表面積測定装置Macsorb1201を用いて行った。前処理は窒素中にて200℃×20分の条件で実施した。平均粒子径(D50)BET比表面積との測定結果を表1に示す。
原料粉末として平均粒子径が0.5μmの三酸化タングステン粉末を用意した。この原料粉末をキャリアガス(Ar)と共にRFプラズマに噴霧し、さらに反応ガスとして酸素を80L/minの流量で流した。この際、反応容器内の圧力は25kPaと減圧側に調整した。このように原料粉末を昇華させながら酸化反応させる昇華工程を経て、酸化タングステン微粒子を作製した。得られた酸化タングステン微粒子の平均粒子径(D50)、比表面積、結晶構造を実施例1と同様にして測定、評価した。その結果を表1に示す。
反応ガスとしてアルゴンを40L/min、空気を40L/minの流量で流し、反応容器内の圧力を40kPaに調整する以外は、実施例2と同様にして昇華工程を実施して酸化タングステン微粒子を作製した。さらに、酸化タングステン微粒子に大気中にて500〜900℃×1〜2hの条件で熱処理を施した。このようにして得た酸化タングステン微粒子(実施例3〜5)の平均粒子径(D50)、比表面積、結晶構造を表1に示す。
プラズマに投入する原料として、FeやMo等の不純物量が多い酸化タングステン粉末を用いる以外は、実施例3と同様の昇華工程と熱処理工程を実施し、Feを300ppm含有する酸化タングステン複合材微粒子を作製した。得られた酸化タングステン複合材微粒子について、平均粒子径(D50)、比表面積、結晶構造を測定、評価した。その結果を表1に示す。さらに、実施例1と同様にしてガラス板上に酸化タングステン複合材微粒子を塗布して試験片を作製し、通常環境下、暗所、可視光照射下で抗菌性能を評価した。抗菌活性値R、RD、RL、RD6h、RL6h、RL1000を表2に示す。実施例6の酸化タングステン複合材微粒子は、実施例3の酸化タングステン微粒子と同様に、通常環境下、暗所、可視光照射下を問わず、高い抗菌性能を示すことが確認された。
実施例3で得られた酸化タングステン粉末に酸化銅(CuO)粉末を1質量%混合した。このようにして得た酸化タングステン複合材粉末について、平均粒子径(D50)、比表面積、結晶構造を測定、評価した。その結果を表1に示す。さらに、実施例1と同様にしてガラス板上に酸化タングステン複合材微粒子を塗布して試験片を作製し、通常環境下、暗所、可視光照射下で抗菌性能を評価した。抗菌活性値R、RD、RL、RD6h、RL6h、RL1000を表2に示す。実施例7の酸化タングステン複合材微粒子は、実施例3の酸化タングステン微粒子と同様に、通常環境下、暗所、可視光照射下を問わず、高い抗菌性能を示すことが確認された。
実施例8においては、プラズマに投入する原料として、酸化タングステン粉末に酸化ジルコニウム粉末を混合して使用する以外は実施例3と同様にして昇華工程と熱処理工程とを実施することによって、ジルコニウム(Zr)を0.1質量%含有する酸化タングステン複合材粉末を作製した。
試薬等として市販されている酸化タングステン粉末(レアメタリック社製)を用いて、実施例1と同様の測定、評価を行った。粉末特性を表1に示す。さらに、実施例1と同様にしてガラス板上に酸化タングステン粉末を塗布したが、粒径が著しく大きいために膜を形成することができず、抗菌性能を評価することはできなかった。
可視光応答型光触媒としての窒素ドープ型酸化チタン粉末の抗菌性能を実施例1と同様にして評価した。粉末特性を表1に、また抗菌性能を表2に示す。窒素ドープ型酸化チタン粉末は、照度が6000lxの可視光を照射しながら24時間保存した場合の抗菌活性値RLは2以上の値を示したものの、通常環境下、暗所、低照度下での抗菌活性値は低く、十分な抗菌性能を得ることはできないことが確認された。
酸化タングステン微粒子や酸化タングステン複合材微粒子を含有する膜の抗菌性能を評価するために、実施例1〜実施例7による微粒子(粉末)を用いて膜を形成した。各粉末を用いて水系分散液を調整し、これらをセラミックス板に塗布して膜を形成した。このような微粒子膜を具備する部材から5×5cmの試験片を切り出して、粉末と同様にして抗菌性能を評価した。その結果を表3に示す。
窒素ドープ型酸化チタン粉末を用いて水系分散液を調整し、これをセラミックス板に塗布することによって、酸化チタン粒子の膜を具備する部材を作製した。このような部材から5×5cmの試験片を切り出して抗菌性能を評価した。その結果を表3に示す。
実施例21においては、実施例3で得られた酸化タングステン粉末を5質量%、硝酸銀をAg換算で0.0005質量%の割合で添加して水系分散液を作製し、光還元処理を行った後にセラミックス板に塗布して膜を形成した。このような膜を具備する部材から5×5cmの試験片を切り出して抗菌性能を評価した。その結果を表3に示す。
Ag系抗菌剤をセラミックス板に塗布した。このような部材から5×5cmの試験片を切り出して抗菌性能を評価した。その結果を表3に示す。
コロイダルシリカをセラミックス板に塗布した。このような部材から5×5cmの試験片を切り出して抗菌性能を評価した。その結果を表3に示す。
抗菌性能の持続性を評価するために、実施例23の部材の抗菌性を成膜直後と通常環境下で6ヶ月保存した後に評価した。抗菌活性値Rはそれぞれ4.2、4.3であり、6ヵ月後においても高い抗菌性能が維持されることが確認された。
比較例4の部材の抗菌性を、Ag系抗菌剤の処理直後と通常環境下で6ヶ月保存した後に評価した。試料作製直後の抗菌活性値Rは4.7であったが、6ヵ月後には抗菌活性値Rが1.7まで低下した。Ag系抗菌剤は初期には高い抗菌性を示すものの、時間の経過と共に抗菌性が低下することが確認された。
実施例3で得られた酸化タングステン粉末0.5mgを5×5cmのガラス板に塗布して試料を作製する以外は、実施例3と同様にして抗菌性能を評価した。酸化タングステン微粒子の付着量は0.02mg/cm2である。その結果、通常環境下、暗所、光照射下のいずれにおいて実施例3と同等の高い抗菌性を示すことが確認された。これは酸化タングステン粉末の粒径が小さく、均一な塗布層を形成することが可能であることから、少量の粉末でも高い抗菌性が得られたものと考えられる。
Claims (20)
- 酸化タングステン微粒子および酸化タングステン複合材微粒子から選ばれる少なくとも1種の微粒子を具備する抗菌性材料であって、
前記微粒子は、JIS−Z−2801(2000)の抗菌加工製品−抗菌性試験方法に準じた方法で、0.02mg/cm2以上40mg/cm2以下の範囲で前記微粒子を付着させた試験片に、黄色ブドウ球菌、大腸菌、肺炎桿菌、緑膿菌、メチシリン耐性黄色ブドウ球菌、および腸管出血性大腸菌から選ばれる少なくとも1種の菌を接種し、24時間保存した後の生菌数を評価する抗菌性評価試験を行ったとき、
R=log(B1/C1)
(式中、B1は無加工試験片を24時間保存した後の生菌数の平均値(個)、C1は前記微粒子を塗布した前記試験片を24時間保存した後の生菌数の平均値(個)である)
で表される抗菌活性値Rが0.1以上であることを特徴とする抗菌性材料。 - 請求項1記載の抗菌性材料において、
前記微粒子は、前記抗菌性評価試験を暗所で行ったとき、
RD=log(BD/CD)
(式中、BDは無加工試験片を暗所で24時間保存した後の生菌数の平均値(個)、CDは前記微粒子を塗布した前記試験片を暗所で24時間保存した後の生菌数の平均値(個)である)
で表される抗菌活性値RDが0.1以上であることを特徴とする抗菌性材料。 - 請求項1記載の抗菌性材料において、
前記微粒子の前記抗菌活性値Rが1以上であることを特徴とする抗菌性材料。 - 請求項2記載の抗菌性材料において、
前記微粒子の前記抗菌活性値RDが1以上であることを特徴とする抗菌性材料。 - 請求項1記載の抗菌性材料において、
前記微粒子の平均一次粒子径(D50)が1nm以上200nm以下の範囲であることを特徴とする抗菌性材料。 - 請求項1記載の抗菌性材料において、
前記微粒子のBET比表面積が4.1m2/g以上820m2/g以下の範囲であることを特徴とする抗菌性材料。 - 請求項1記載の抗菌性材料において、
前記微粒子はX線回折法で測定したとき、2θが22.5°以上25°以下の範囲に第1ピーク、第2ピーク、および第3ピークを有することを特徴とする抗菌性材料。 - 請求項1記載の抗菌性材料において、
前記微粒子は、白色蛍光灯と紫外線カットフィルタを使用し、波長が380nm以上のみで照度が6000lxの可視光を、前記試験片に照射した状態で、前記抗菌性評価試験を行ったとき、
RL=log(BL/CL)
(式中、BLは無加工試験片を前記可視光下で24時間保存した後の生菌数の平均値(個)、CLは前記微粒子を塗布した前記試験片を前記可視光下で24時間保存した後の生菌数の平均値(個)である)
で表される抗菌活性値RLが1.0以上であることを特徴とする抗菌性材料。 - 請求項1記載の抗菌性材料において、
前記酸化タングステン複合材は遷移金属元素を0.01質量%以上50質量%以下の範囲で含むことを特徴とする抗菌性材料。 - 請求項1記載の抗菌性材料において、
前記酸化タングステン複合材はTi、Zr、Mn、Fe、Pd、Pt、Cu、Ag、Zn、AlおよびCeから選ばれる少なくとも1種の金属元素を0.001質量%以上50質量%以下の範囲で含むことを特徴とする抗菌性材料。 - 請求項1記載の抗菌性材料において、
前記酸化タングステン複合材はCu、AgおよびZnから選ばれる少なくとも1種の金属元素を0.001質量%以上1質量%以下の範囲で含むことを特徴とする抗菌性材料。 - 請求項10記載の抗菌性材料において、
前記金属元素は、単体、化合物、および酸化タングステンとの複合化合物から選ばれる少なくとも1種の形態で、前記酸化タングステン複合材に含まれることを特徴とする抗菌性材料。 - 請求項1記載の抗菌性材料を具備することを特徴とする抗菌性膜。
- 請求項13記載の抗菌性膜において、
前記抗菌性膜は5質量%以上95質量%以下の範囲の無機バインダを含有することを特徴とする抗菌性膜。 - 請求項13記載の抗菌性膜において、
膜厚が2nm以上1000nm以下の範囲であることを特徴とする抗菌性膜。 - 請求項1記載の抗菌性材料を具備することを特徴とする抗菌性部材。
- 請求項13記載の抗菌性膜を具備することを特徴とする抗菌性部材。
- 請求項17記載の抗菌性部材でおいて、
照度が1000lx以下の可視光の照射下で用いられることを特徴とする抗菌性部材。 - 請求項18記載の抗菌性部材でおいて、
暗所で用いられることを特徴とする抗菌性部材。 - 請求項19記載の抗菌性部材において、
黄色ブドウ球菌、大腸菌、肺炎桿菌、緑膿菌、メチシリン耐性黄色ブドウ球菌、および腸管出血性大腸菌から選ばれる少なくとも1種の菌に対して抗菌性能を示す部材として使用されることを特徴とする抗菌性部材。
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10327445B2 (en) * | 2009-08-12 | 2019-06-25 | Kabushiki Kaisha Toshiba | Antiviral material, antiviral film, antiviral fiber, and antiviral product |
Families Citing this family (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US9072396B1 (en) * | 2009-03-31 | 2015-07-07 | Bellamat Llc | Antimicrobial screening runner and mat |
CN105980056B (zh) * | 2013-12-06 | 2018-08-24 | 独立行政法人产业技术综合研究所 | 包含添加有铋的氧化钨光催化剂的抗真菌及抗细菌材料 |
DE102013114575A1 (de) * | 2013-12-19 | 2015-06-25 | AMiSTec GmbH & Co. KG | Verfahren zum Herstellen eines antimikrobiell wirksamen Verbundwerkstoffs und antimikrobiell wirksamer Verbundwerkstoff |
KR20150119755A (ko) * | 2014-04-16 | 2015-10-26 | 삼성전자주식회사 | 항균커버 및 이를 구비한 전자장치 |
FR3022785B1 (fr) * | 2014-06-25 | 2017-10-13 | Pylote | Utilisation de materiaux incorporant des microparticules pour eviter la proliferation de contaminants. |
JP6457301B2 (ja) * | 2015-03-06 | 2019-01-23 | 株式会社東芝 | 光触媒構造体およびその製造方法および光触媒分散液 |
WO2017161423A1 (en) * | 2016-03-24 | 2017-09-28 | Monash University | Smart window coating |
JP7288709B2 (ja) * | 2017-05-19 | 2023-06-08 | 株式会社希少金属材料研究所 | 可視光応答型光触媒のタングステン化合物及び塗料 |
CN111133270A (zh) * | 2017-07-19 | 2020-05-08 | Lg电子株式会社 | 热交换器 |
US10882030B2 (en) * | 2017-08-25 | 2021-01-05 | Uop Llc | Crystalline transition metal tungstate |
JP6953965B2 (ja) * | 2017-09-29 | 2021-10-27 | 信越化学工業株式会社 | 抗菌・抗カビ性を有する光触媒・合金微粒子分散液、その製造方法、及び光触媒・合金薄膜を表面に有する部材 |
KR102159032B1 (ko) * | 2018-09-12 | 2020-09-23 | (주) 화진산업 | 고타이트가 함유된 광경화형 항균 코팅 필름의 제조방법 및 이에 따라 제조된 항균 코팅 필름 |
JP7474072B2 (ja) * | 2020-03-03 | 2024-04-24 | シャープ株式会社 | 光触媒コーティング剤及びスプレー製品 |
USD1027361S1 (en) | 2022-07-20 | 2024-05-21 | Blue Buffalo Enterprises, Inc. | Pet dental treat |
CN115958192A (zh) * | 2023-01-09 | 2023-04-14 | 东北大学 | 一种高效抗菌的高熵合金纳米颗粒及其制备方法与应用 |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH06293611A (ja) * | 1993-04-05 | 1994-10-21 | Asahi Chem Ind Co Ltd | 抗菌性材料 |
JPH08296031A (ja) * | 1995-04-24 | 1996-11-12 | Toppan Printing Co Ltd | 金属酸化物被覆体とその製造方法 |
JP2004300648A (ja) * | 2002-11-14 | 2004-10-28 | Toto Ltd | 機能性壁紙 |
WO2006025470A1 (ja) * | 2004-08-31 | 2006-03-09 | Sumitomo Metal Mining Co., Ltd. | 導電性粒子、可視光透過型粒子分散導電体およびその製造方法、透明導電薄膜およびその製造方法、これを用いた透明導電物品、赤外線遮蔽物品 |
WO2007088891A1 (ja) * | 2006-02-01 | 2007-08-09 | Toshiba Materials Co., Ltd. | 光触媒材料およびそれを用いた光触媒組成物並びに光触媒製品 |
JP5546769B2 (ja) * | 2008-01-28 | 2014-07-09 | 株式会社東芝 | 可視光応答型光触媒粉末とそれを用いた可視光応答型の光触媒材料、光触媒塗料、光触媒製品 |
Family Cites Families (25)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS60181002A (ja) | 1984-02-29 | 1985-09-14 | Kanebo Ltd | ゼオライトを担体とする抗菌性組成物およびその製造方法 |
JP2662986B2 (ja) * | 1988-06-24 | 1997-10-15 | 高周波熱錬株式会社 | タングステンもしくは酸化タングステン超微粒子の製造方法 |
JP2790596B2 (ja) | 1993-06-17 | 1998-08-27 | 株式会社竹中工務店 | 院内感染防止方法 |
US6832735B2 (en) * | 2002-01-03 | 2004-12-21 | Nanoproducts Corporation | Post-processed nanoscale powders and method for such post-processing |
US6933331B2 (en) * | 1998-05-22 | 2005-08-23 | Nanoproducts Corporation | Nanotechnology for drug delivery, contrast agents and biomedical implants |
JP2001081409A (ja) | 1999-09-14 | 2001-03-27 | Daido Steel Co Ltd | 抗菌コート剤、抗菌剤、及び院内感染防止方法 |
JP2001152130A (ja) * | 1999-11-25 | 2001-06-05 | Toto Ltd | 光触媒性親水性部材、および、その製造方法 |
US6653356B2 (en) * | 1999-12-13 | 2003-11-25 | Jonathan Sherman | Nanoparticulate titanium dioxide coatings, and processes for the production and use thereof |
JP3717868B2 (ja) * | 2001-08-30 | 2005-11-16 | 東陶機器株式会社 | 光触媒性コーティング剤及び光触媒性複合材並びにその製造方法 |
JP3945765B2 (ja) * | 2002-09-04 | 2007-07-18 | 東彦 山口 | 多機能木質材料およびその製造方法 |
JP2004195439A (ja) * | 2002-12-20 | 2004-07-15 | Jfe Steel Kk | 光触媒およびその製造方法 |
US7591984B2 (en) * | 2003-07-28 | 2009-09-22 | Los Alamos National Security, Llc | Preparation of tungsten oxide |
JP4507066B2 (ja) * | 2004-02-18 | 2010-07-21 | 多木化学株式会社 | 酸化タングステン含有酸化チタンゾル及びその製造方法並びにコーティング剤及び光機能体 |
JP2006055697A (ja) * | 2004-08-17 | 2006-03-02 | Tokyo Institute Of Technology | 分散体 |
CN101023498B (zh) * | 2004-08-31 | 2012-02-29 | 住友金属矿山株式会社 | 导电性粒子、可见光透过型粒子分散导电体及其制造方法、透明导电薄膜及其制造方法、使用它的透明导电物品、红外线屏蔽物品 |
JP4355945B2 (ja) * | 2004-11-08 | 2009-11-04 | 住友金属鉱山株式会社 | 近赤外線吸収繊維およびこれを用いた繊維製品 |
JP2006131583A (ja) * | 2004-11-09 | 2006-05-25 | Marukatsu Sangyo Kk | 抗菌性付与剤 |
US20080119352A1 (en) * | 2005-01-18 | 2008-05-22 | Shinya Kitaguchi | Visible Light-Responsive Photocatalyst Composition and Process for Producing the Same |
US7438948B2 (en) * | 2005-03-21 | 2008-10-21 | Ppg Industries Ohio, Inc. | Method for coating a substrate with an undercoating and a functional coating |
JP2008006429A (ja) * | 2006-02-01 | 2008-01-17 | Toshiba Lighting & Technology Corp | 光触媒材料、光触媒体、光触媒製品、照明器具及び光触媒材料の製造方法 |
TW200732036A (en) * | 2006-02-01 | 2007-09-01 | Toshiba Lighting & Technology | Photocatalysis material, photocatalysis body, photocatalysis product, luminaire and manufacturing method thereof |
GB0603138D0 (en) * | 2006-02-16 | 2006-03-29 | Queen Mary & Westfield College | Virucidal materials |
JP5306181B2 (ja) * | 2007-03-23 | 2013-10-02 | 株式会社東芝 | 光触媒用三酸化タングステン粉末の製造方法、光触媒用三酸化タングステン粉末および光触媒製品 |
JP5362570B2 (ja) * | 2007-09-05 | 2013-12-11 | 株式会社東芝 | 可視光応答型光触媒粉末とそれを用いた可視光応答型の光触媒材料、光触媒塗料および光触媒製品 |
EP2248586B1 (en) | 2008-01-28 | 2020-07-29 | Kabushiki Kaisha Toshiba | Visible light response-type photocatalyst powder, visible light response-type photocatalyst material using the visible light response-type photocatalyst powder, photocatalyst coating material, and photocatalyst product |
-
2009
- 2009-03-04 EP EP09717571.5A patent/EP2255878B1/en active Active
- 2009-03-04 JP JP2010501800A patent/JP5957175B2/ja active Active
- 2009-03-04 WO PCT/JP2009/000981 patent/WO2009110233A1/ja active Application Filing
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- 2010-09-02 US US12/874,849 patent/US20110052662A1/en not_active Abandoned
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- 2015-02-12 JP JP2015025563A patent/JP5959675B2/ja active Active
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- 2020-05-12 US US16/872,554 patent/US11896966B2/en active Active
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH06293611A (ja) * | 1993-04-05 | 1994-10-21 | Asahi Chem Ind Co Ltd | 抗菌性材料 |
JPH08296031A (ja) * | 1995-04-24 | 1996-11-12 | Toppan Printing Co Ltd | 金属酸化物被覆体とその製造方法 |
JP2004300648A (ja) * | 2002-11-14 | 2004-10-28 | Toto Ltd | 機能性壁紙 |
WO2006025470A1 (ja) * | 2004-08-31 | 2006-03-09 | Sumitomo Metal Mining Co., Ltd. | 導電性粒子、可視光透過型粒子分散導電体およびその製造方法、透明導電薄膜およびその製造方法、これを用いた透明導電物品、赤外線遮蔽物品 |
WO2007088891A1 (ja) * | 2006-02-01 | 2007-08-09 | Toshiba Materials Co., Ltd. | 光触媒材料およびそれを用いた光触媒組成物並びに光触媒製品 |
JP5546769B2 (ja) * | 2008-01-28 | 2014-07-09 | 株式会社東芝 | 可視光応答型光触媒粉末とそれを用いた可視光応答型の光触媒材料、光触媒塗料、光触媒製品 |
Non-Patent Citations (3)
Title |
---|
BAMWENDA, G. R. ET AL: "The visible light induced photocatalytic activity of tungsten trioxide powders", APPLIED CATALYSIS A: GENERAL, vol. Vol.210, No.1-2, JPN6013064463, 23 February 2001 (2001-02-23), pages 181 - 191, ISSN: 0002716259 * |
TATSUMA, T. ET AL: "Bactericidal effect of an energy storage TiO2-WO3 photocatalyst in dark", ELECTROCHEMISTRY COMMUNICATIONS, vol. 5, no. 9, JPN6013064465, 23 August 2003 (2003-08-23), pages 793 - 796, XP002656981, ISSN: 0002716261, DOI: 10.1016/j.elecom.2003.07.003 * |
立間徹,外: "エネルギー貯蔵型光触媒とその応用", 表面科学, vol. 24, no. 1, JPN6013064464, 10 January 2003 (2003-01-10), pages 13 - 18, ISSN: 0002716260 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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US10327445B2 (en) * | 2009-08-12 | 2019-06-25 | Kabushiki Kaisha Toshiba | Antiviral material, antiviral film, antiviral fiber, and antiviral product |
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US20110052662A1 (en) | 2011-03-03 |
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TWI404569B (zh) | 2013-08-11 |
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