JP5754893B2 - Photocatalytic sheet and virus infection prevention or patient mask using the same - Google Patents
Photocatalytic sheet and virus infection prevention or patient mask using the same Download PDFInfo
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- JP5754893B2 JP5754893B2 JP2010117084A JP2010117084A JP5754893B2 JP 5754893 B2 JP5754893 B2 JP 5754893B2 JP 2010117084 A JP2010117084 A JP 2010117084A JP 2010117084 A JP2010117084 A JP 2010117084A JP 5754893 B2 JP5754893 B2 JP 5754893B2
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Landscapes
- Respiratory Apparatuses And Protective Means (AREA)
- Catalysts (AREA)
Description
本発明は、ウイルスを不活化する光触媒シート及び該光触媒シートを用いたウイルス感染予防又は患者用マスクに関する。より詳しくは、本発明は、インフルエンザウイルスなどのエンベロープをもつウイルスの感染を予防するために有効な光触媒シート及び該光触媒シートを用いた感染予防又は患者用マスクに関する。 The present invention relates to a photocatalyst sheet for inactivating viruses and a virus infection prevention or patient mask using the photocatalyst sheet. More specifically, the present invention relates to a photocatalyst sheet effective for preventing infection with a virus having an envelope such as influenza virus, and an infection prevention or patient mask using the photocatalyst sheet.
光触媒は、３８０ｎｍ以下の紫外線照射下でヒドロキシラジカルを発生することによる有機物分解効果により、消臭、抗菌効果、ウイルス不活化効果が期待でき、マスクやフィルターなどへ利用されている。
以下の特許文献１、特許文献２、特許文献３には、ウイルスの感染防止、除去などを謳った光触媒を応用したフィルターや物品が報告されている。
The photocatalyst can be expected to have a deodorizing effect, an antibacterial effect, and a virus inactivating effect due to an organic substance decomposing effect by generating a hydroxy radical under irradiation with ultraviolet rays of 380 nm or less, and is used for a mask or a filter.
In the following Patent Literature 1, Patent Literature 2, and Patent Literature 3, filters and articles using photocatalysts that prevent and remove viruses are reported.
特許文献１には、可視光応答型光触媒によりウイルスの感染力を低下させる光触媒含有体が開示されている。この技術によれば光の存在下ウイルスの感染力を低下させることができるが、光の無いところでは効果を発揮しない。 Patent Document 1 discloses a photocatalyst-containing body that reduces the infectivity of a virus with a visible light responsive photocatalyst. According to this technique, the infectivity of a virus can be reduced in the presence of light, but the effect is not exhibited in the absence of light.
特許文献２には、アパタイトの結晶構造中に光触媒機能を有する金属原子が置換等され結晶構造中に取り込まれた光触媒が提案されている。この光触媒は、アパタイトの蛋白質親和性を利用したウイルスの吸着機能を謳っているが、加工時に光触媒が凝集し、２次粒子径として１〜１０μｍの粒子径分布を有しているため、極細繊維層を有する基材に担持させると目詰まりを起こし、圧損が高くなり易い。 Patent Document 2 proposes a photocatalyst in which a metal atom having a photocatalytic function is substituted in the crystal structure of apatite and incorporated in the crystal structure. This photocatalyst has a function of adsorbing viruses utilizing the protein affinity of apatite, but the photocatalyst aggregates during processing and has a particle size distribution of 1 to 10 μm as the secondary particle size. When it is supported on a substrate having a layer, clogging occurs and pressure loss tends to increase.
特許文献３には、カテキンと光触媒が併用されたフィルターが開示されている。光環境下カテキンの抗酸化力と光触媒の酸化力が相乗的に作用し、ウイルス除去機能が得られると記載されている。しかしながら、このフィルターはウイルス吸着機能が無く、光が存在しない場合にはウイルス除去機能が得られない。 Patent Document 3 discloses a filter in which catechin and a photocatalyst are used in combination. It is described that the anti-oxidant power of catechin and the oxidizing power of the photocatalyst act synergistically in a light environment to obtain a virus removal function. However, this filter does not have a virus adsorption function, and a virus removal function cannot be obtained in the absence of light.
一方、従来からあるウイルス感染防止マスクに関しては、米国の疾病管理予防センターの医療施設における結核感染防止のためのガイドラインに基づき、労働安全衛生局により定められたＮ９５規格がある。
Ｎ９５規格に適合したマスクは、かつて流行したＳＡＲＳ（重症性呼吸器症候群）ウイルスに対し感染リスクを低減することが知られている。しかしながら、Ｎ９５規格適合マスクは、病原菌やウイルスを含む飛沫などを捕集するのみであり、マスクの表面を触ることにより手などに付着し、２次感染をおこす恐れがあった。
On the other hand, with regard to conventional virus infection prevention masks, there is the N95 standard established by the Bureau of Occupational Safety and Health based on guidelines for prevention of tuberculosis infection in medical facilities of the Center for Disease Control and Prevention in the United States.
Masks conforming to the N95 standard are known to reduce the risk of infection against the once prevalent SARS (Severe Respiratory Syndrome) virus. However, the N95 standard compliant mask only collects droplets containing pathogenic bacteria and viruses, and may adhere to the hand etc. by touching the surface of the mask and cause secondary infection.
これらを解消する手段として銀イオンを付与した抗菌シートを積層したり、以下の特許文献４に示すように光触媒を添着させたシートを積層し、マスクに使用されるようになってきた。
特許文献４には、二酸化チタンアパタイト光触媒を添着した感染予防マスクが開示されている。このマスクは、特許文献２に開示されている光触媒をマスクに応用した例であって、特許文献４には、該マスクは、ヒドロキシアパタイトの蛋白質親和性の機能を利用し、病原体を吸着し、光触媒の機能により分解すると記載されている。しかしながら、特許文献４には、ウイルスを吸着し、吸着したウイルスが再汚染しないという試験結果が開示されておらず、使用済みのマスクの表面を手で触っても安全なものであるとはいえない。
As means for solving these problems, an antibacterial sheet provided with silver ions is laminated, or a sheet to which a photocatalyst is attached is laminated as shown in Patent Document 4 below, and has been used as a mask.
Patent Document 4 discloses an infection prevention mask to which a titanium dioxide apatite photocatalyst is attached. This mask is an example in which the photocatalyst disclosed in Patent Document 2 is applied to a mask. In Patent Document 4, the mask uses a protein affinity function of hydroxyapatite to adsorb a pathogen, It is described that it decomposes by the function of the photocatalyst. However, Patent Document 4 does not disclose a test result that adsorbs a virus and does not recontaminate the adsorbed virus, and it can be said that it is safe to touch a used mask surface with a hand. Absent.
本発明が解決しようとする課題は、光触媒のＵＶ光による有機物分解効果から得られるウイルスの不活化効果に加え、インフルエンザウイルスのようなエンベロープを持つウイルスに対しては光の存在しない空間や夜間でも強力な吸着性能を持つ光触媒シートを提供すること、そして該光触媒シートをマスクを構成する部材として用いることにより感染リスクを低減することができるウイルス感染予防マスクを提供することである。 The problem to be solved by the present invention is that in addition to the virus inactivation effect obtained from the organic substance decomposition effect by UV light of the photocatalyst, the virus having an envelope such as influenza virus can be used even in a space where there is no light or at night. It is to provide a photocatalyst sheet having a strong adsorption performance, and to provide a virus infection prevention mask that can reduce the risk of infection by using the photocatalyst sheet as a member constituting the mask.
本発明者らは、鋭意検討し、実験を重ねた結果、表面修飾した光触媒を表面に担持した特定の不織布に予めＵＶ照射を行うことによりインフルエンザウイルスのようなエンベロープを持つウイルスが該不織布に選択的に吸着されることを発見し、本発明を完成するに至った。 As a result of intensive studies and experiments, the inventors selected a nonwoven fabric having an envelope such as influenza virus by pre-irradiating UV onto a specific nonwoven fabric carrying a surface-modified photocatalyst on the surface. The present invention has been completed.
すなわち、本発明は、以下の通りのものであります：
［１］目付１０〜２００ｇ／ｍ２の不織布にケイ素化合物で表面修飾された酸化チタン光触媒を０．１〜１０ｇ／ｍ２で担持させた、比表面積が２〜２０ｍ２／ｇである光触媒シート。
That is, the present invention is as follows:
[1] A photocatalytic sheet having a specific surface area of 2 to 20 m 2 / g, in which a titanium oxide photocatalyst surface-modified with a silicon compound is supported at 0.1 to 10 g / m 2 on a nonwoven fabric having a basis weight of 10 to 200 g / m 2. .
［２］３４０ｎｍ〜３８０ｎｍの波長を含む光で照射処理された、前記［１］に記載の光触媒シート。 [2] The photocatalyst sheet according to [1], which is irradiated with light having a wavelength of 340 nm to 380 nm.
［３］前記不織布は、平均繊維径０．５〜５．０μｍであり、かつ、目付１〜２０ｇ／ｍ２であるメルトブロウン繊維層とスパンボンド繊維層をそれぞれ少なくとも１層以上含む構造を有する不織布である、前記［１］又は［２］に記載の光触媒シート。 [3] The nonwoven fabric has an average fiber diameter of 0.5 to 5.0 μm and a structure including at least one meltblown fiber layer and a spunbond fiber layer each having a basis weight of 1 to 20 g / m 2. The photocatalyst sheet according to [1] or [2], which is a nonwoven fabric.
［４］前記不織布は、ポリエステル系繊維又はポリアミド系繊維からなる、前記［１］〜［３］のいずれかに記載の光触媒シート。 [4] The photocatalyst sheet according to any one of [1] to [3], wherein the nonwoven fabric is made of polyester fiber or polyamide fiber.
［５］前記不織布は、アクリル系樹脂により前処理されている、前記［１］〜［４］のいずれかに記載の光触媒シート。 [5] The photocatalyst sheet according to any one of [1] to [4], wherein the nonwoven fabric is pretreated with an acrylic resin.
［６］マスク本体と該マスク本体の両端部に耳かけ部とを備えるマスクにおいて、該マスク本体は少なくとも３層の不織布の積層体からなり、最外層が、目付１０〜７０ｇ／ｍ２である前記［１］〜［５］のいずれかに記載の光触媒シートであることを特徴とする前記マスク。 [6] In a mask provided with a mask body and ear hooks at both ends of the mask body, the mask body is composed of a laminate of at least three layers of nonwoven fabric, and the outermost layer has a basis weight of 10 to 70 g / m 2 . The photomask sheet according to any one of [1] to [5], wherein the mask.
［７］マスク本体と該マスク本体の両端部に耳かけ部とを備えるマスクにおいて、該マスク本体は少なくとも４層の不織布の積層体からなり、中間層として、帯電加工したメルトブロウン不織布と、目付１０〜７０ｇ／ｍ２である前記［１］〜［５］のいずれかに記載の光触媒シートを、それぞれ少なくとも１つ有し、該帯電加工したメルトブロウン不織布層は、該光触媒シートよりも外側に配置されていることを特徴とする前記マスク。 [7] In a mask having a mask body and ear hooks at both ends of the mask body, the mask body is made of a laminate of at least four layers of nonwoven fabric, and an intermediate layer is formed with a charged melt-blown nonwoven fabric and a basis weight. Each of the photocatalyst sheets according to any one of [1] to [5], which is 10 to 70 g / m 2 , has at least one photocatalyst sheet, and the melt-blown nonwoven fabric layer that has been subjected to the charge processing is disposed outside the photocatalyst sheet. The mask, which is arranged.
［８］マスクの形状が折りたたみ型、カップ型又はフラット型である、前記［６］又は［７］に記載のマスク。 [8] The mask according to [6] or [7], wherein the shape of the mask is a folding type, a cup type, or a flat type.
本発明の光触媒シートは、光触媒のＵＶ光による有機物分解効果に因るウイルスの不活化効果、抗菌効果、消臭効果に加え、インフルエンザウイルスのようなエンベロープを持つウイルスに対しては光の存在しない空間や夜間でも強力な吸着性能を持つため、シートに触れることによる２次感染リスクを低減する効果に優れる。また、該光触媒シートをマスクを構成する部材に用いることにより、感染リスクを低減することができるウイルス感染予防マスクを提供することができる。 The photocatalyst sheet of the present invention has no light for viruses having an envelope such as influenza virus in addition to the virus inactivation effect, antibacterial effect, and deodorization effect due to the organic substance decomposition effect by UV light of the photocatalyst. Because it has strong adsorption performance in space and at night, it is excellent in reducing the risk of secondary infection caused by touching the sheet. Moreover, the virus infection prevention mask which can reduce an infection risk can be provided by using this photocatalyst sheet for the member which comprises a mask.
本発明の光触媒シートに使用する光触媒は、特許第４２１２２４２号に記載されている方法により製造することができる。この製造方法では、酸化チタンよりなる光触媒粒子を、脱水素縮合触媒の存在下、以下の式（１）：
−（Ｒ１Ｒ２ＳｉＯ）− （１）
｛式中、Ｒ１、及びＲ２は、各々独立して、水素原子、直鎖状又は分枝上の炭素数１〜３０個のアルキル基、炭素数５〜２０のシクロアルキル基、あるいは置換されていないか又は炭素数１〜２０のアルキル基、炭素数１〜２０のアルコキシ基若しくはハロゲン原子で置換されている炭素数６〜２０のアリール基を表す。｝で表されるモノオキシジオルガノシラン単位と、以下の式（２）：
-(R 1 R 2 SiO)-(1)
{Wherein R 1 and R 2 are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, or a substituted group. Or an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms substituted with a halogen atom. } And the following formula (2):
Ｓｉ−Ｈ基含有ケイ素化合物との反応後の変性酸化チタン光触媒の体積平均粒子径は、好ましくは１０ｎｍ〜１００ｎｍ、より好ましくは１０〜５０ｎｍ、更に好ましくは１０〜３０ｎｍである。１００ｎｍを越える粒径を持つ場合には不織布シートを構成する繊維の表層を被覆する光触媒層の厚みが大きくなり、好ましくない。
また、特許第４２１２２４２に記載されている方法の中で、原料である酸化チタンの体積平均粒子径に対し、変性後の酸化チタン光触媒の体積平均粒子径の増加量は３０ｎｍ以下であることが好ましい。体積平均粒子径の増加量が３０ｎｍを超える場合は、ケイ素化合物の層が厚いため、後述するＵＶ照射処理に時間がかかり好ましくない。
The volume average particle diameter of the modified titanium oxide photocatalyst after reaction with the Si—H group-containing silicon compound is preferably 10 nm to 100 nm, more preferably 10 to 50 nm, and still more preferably 10 to 30 nm. When the particle diameter exceeds 100 nm, the thickness of the photocatalyst layer covering the surface layer of the fibers constituting the nonwoven fabric sheet becomes unfavorable.
Further, in the method described in Japanese Patent No. 4212242, the amount of increase in the volume average particle size of the modified titanium oxide photocatalyst is preferably 30 nm or less with respect to the volume average particle size of titanium oxide as a raw material. . When the amount of increase in the volume average particle diameter exceeds 30 nm, the silicon compound layer is thick, and therefore it is not preferable because it takes time for the UV irradiation treatment described later.
光触媒シートに用いる不織布の素材としては、綿、レーヨン、キュプラなどのセルロース系繊維、ナイロン６、ナイロン６６などのポリアミド系繊維、ポリエチレンテレフタレート、ポリブチレンテレフタレート等のポリエステル系繊維、ポリプロピレン、ポリエチレン等のポリオレフィン系繊維、アクリル繊維などの熱可塑性繊維が用いられる。これらの繊維は単独で用いても、２種以上を混用、複合、積層して用いてもよい。 Nonwoven fabric materials used for the photocatalyst sheet include cellulose fibers such as cotton, rayon and cupra, polyamide fibers such as nylon 6 and nylon 66, polyester fibers such as polyethylene terephthalate and polybutylene terephthalate, and polyolefins such as polypropylene and polyethylene. Thermoplastic fibers such as system fibers and acrylic fibers are used. These fibers may be used alone or in combination of two or more, combined, or laminated.
光触媒のＵＶ光によるウイルス不活化効果はヒドロキラジカル生成による有機物分解効果に因るため、使用される環境状態にもよるが基材の水分率が高いほど性能が向上する傾向にある。このため、光触媒のＵＶ光によるウイルス不活化効果は、素材としてのセルロース繊維、ナイロン繊維、ポリエステル繊維、ポリオレフィン繊維の順に性能が向上する。光触媒のＵＶ光によるウイルス不活化効果に関しては、水分率の低い素材であっても、改質、後加工等により親水性を向上させることにより効果を向上させることができるが、ウイルス吸着効果は基材の水分率には影響されずこの限りではない。 The virus inactivation effect of the photocatalyst by UV light is due to the organic matter decomposition effect due to the generation of hydroxyl radicals. Therefore, the higher the moisture content of the base material, the higher the performance, although it depends on the environmental conditions used. For this reason, the virus inactivation effect by UV light of a photocatalyst improves in order of cellulose fiber, nylon fiber, polyester fiber, and polyolefin fiber as materials. With regard to the virus inactivation effect of UV light from the photocatalyst, even if the material has a low moisture content, the effect can be improved by improving the hydrophilicity by modification, post-processing, etc. This is not limited by the moisture content of the material.
繊維の断面形状は丸断面、異形断面など選択できるが、より比表面積の大きくなる異形断面も好ましく用いることができる。
光触媒シートに使われる不織布の製法については、スパンボンド法、サーマルボンド法、スパンレース法、ニードルパンチ法、メルトブロウン法、ケミカルボンド法などいずれでもよく、用途に適した製法を使用すればよい。
The cross-sectional shape of the fiber can be selected from a round cross-section and an irregular cross-section, but an irregular cross-section having a larger specific surface area can also be preferably used.
The nonwoven fabric used for the photocatalyst sheet may be produced by any method such as a spunbond method, a thermal bond method, a spunlace method, a needle punch method, a melt blown method, or a chemical bond method, and a production method suitable for the application may be used.
本発明の光触媒シートの目付は１０〜２００ｇ／ｍ２であり、好ましくは１０〜１００ｇ／ｍ２である。後述するように光触媒は予めＵＶ照射することにより、比表面積が大きくなり、ウイルスの吸着性能が向上する。このため、不織布の目付が２００ｇを超えると照射したＵＶ光が不織布の厚み方向中央部まで届きにくく、ＵＶ照射時間が長くなりコストアップにつながる。本発明の光触媒シートの目付は、より好ましくは１０〜７０ｇ／ｍ２である。 The basis weight of the photocatalyst sheet of the present invention is 10 to 200 g / m 2 , preferably 10 to 100 g / m 2 . As will be described later, the photocatalyst is preliminarily irradiated with UV to increase the specific surface area and improve the virus adsorption performance. For this reason, when the fabric weight of the nonwoven fabric exceeds 200 g, the irradiated UV light hardly reaches the central portion in the thickness direction of the nonwoven fabric, and the UV irradiation time becomes longer, leading to an increase in cost. The basis weight of the photocatalyst sheet of the present invention is more preferably 10 to 70 g / m 2 .
本発明の光触媒シートは、予めＵＶ光を照射することにより比表面積が大きくなり、ウイルス吸着効果が向上するが、不織布基材自体の比表面積が大きいほど効果が高くなる。そのため、光触媒シートに用いる不織布の構造としては、極細繊維層を有する不織布がウイルスを含む飛沫の捕捉性、ウイルスの吸着性の観点で好ましい。光触媒シート基材としては、メルトブロウン繊維層とスパンボンド繊維層をそれぞれ少なくとも１層以上含む構造を有する不織布であることが好ましい。例えば、スパンボンド／メルトブロウン／メルトブロウン／スパンボンド（ＳＭＭＳ）不織布、スパンボンド／メルトブロウン／スパンボンド（ＳＭＳ）不織布、スパンボンド／メルトブロウン（ＳＭ）不織布、スパンボンド不織布、サーマルボンド不織布が挙げられるが、なかでも極細繊維層を有するＳＭＭＳ、ＳＭＳ、ＳＭ構造を持つ不織布が好ましく用いられる。 The photocatalyst sheet of the present invention has a specific surface area that is increased by irradiating UV light in advance, and the virus adsorption effect is improved. However, the effect increases as the specific surface area of the nonwoven fabric substrate itself increases. Therefore, as a structure of the nonwoven fabric used for the photocatalyst sheet, a nonwoven fabric having an ultrafine fiber layer is preferable from the viewpoints of catching droplets containing viruses and adsorbing viruses. The photocatalyst sheet base material is preferably a non-woven fabric having a structure including at least one meltblown fiber layer and at least one spunbond fiber layer. Examples include spunbond / meltblown / meltblown / spunbond (SMMS) nonwoven fabric, spunbond / meltblown / spunbond (SMS) nonwoven fabric, spunbond / meltblown (SM) nonwoven fabric, spunbond nonwoven fabric, and thermal bond nonwoven fabric. Of these, non-woven fabrics having an SMMS, SMS, or SM structure having an ultrafine fiber layer are preferably used.
光触媒シートにおいて光触媒の担持量は、０．１〜１０ｇ／ｍ２、好ましくは０．１〜５ｇ／ｍ２、より好ましくは０．５〜５ｇ／ｍ２である。光触媒０．１〜１０ｇ／ｍ２の付着量は、不織布基材に予め添加されているＴｉのＸ線強度を差し引いて２〜２００ｋｃｐｓに相当するＴｉのＸ線強度が得られる。光触媒シートにおいて光触媒の担持量が０．１ｇ／ｍ２以下では、インフルエンザウイルスの吸着性及び光触媒の有機物分解効果によるウイルスの不活化効果が弱くなり、不十分であり、一方、１０ｇ／m2を超える担持を行っても有効な増量効果が得られず好ましくない。光触媒粒子は均一に薄く繊維表面にコーティングされていることにより、最も効率よく効果が発揮でき、多層に厚くコーティングされていても担持量に見合う効果の向上は得られない。かかる観点から、光触媒の好ましい担持量は０．１〜５ｇ／ｍ２である。 In the photocatalyst sheet, the supported amount of the photocatalyst is 0.1 to 10 g / m 2 , preferably 0.1 to 5 g / m 2 , and more preferably 0.5 to 5 g / m 2 . The adhesion amount of 0.1 to 10 g / m 2 of the photocatalyst is obtained by subtracting the X-ray intensity of Ti previously added to the nonwoven fabric substrate to obtain an X-ray intensity of Ti corresponding to 2 to 200 kcps. If the amount of the photocatalyst supported in the photocatalyst sheet is 0.1 g / m 2 or less, the inactivation effect of the virus due to the adsorbability of influenza virus and the organic matter decomposition effect of the photocatalyst is weak and insufficient, while 10 g / m 2 is reduced. Even if it exceeds the carrying amount, an effective weight increasing effect cannot be obtained, which is not preferable. Since the photocatalyst particles are uniformly and thinly coated on the fiber surface, the effect can be exhibited most efficiently, and even if the multilayer is thickly coated, an improvement in the effect commensurate with the carrying amount cannot be obtained. From such a viewpoint, the preferable loading amount of the photocatalyst is 0.1 to 5 g / m 2 .
不織布を構成する繊維の繊径は、用途に応じて選択すればよいが、光触媒のウイルス不活化及び吸着性能の観点から、より細いほうが好ましい。
本発明の光触媒シートの加工としては、Ｄｉｐ−Ｎｉｐ法、グラビア印刷法、スプレー法など従来の方法で光触媒を担持させることができる。なかでもスプレー法は基材を圧縮すること無く光触媒を担持させることができ、特にマスク、フィルター用途に使用する場合などは圧力損失への影響が小さくなるため好ましい。具体的なスプレー染色法としては、ローターダンブニング法等が挙げられる。
The fiber diameter of the fibers constituting the nonwoven fabric may be selected according to the use, but a thinner one is preferable from the viewpoint of virus inactivation and adsorption performance of the photocatalyst.
As processing of the photocatalyst sheet of the present invention, the photocatalyst can be supported by a conventional method such as a Dip-Nip method, a gravure printing method, or a spray method. Of these, the spray method is preferable because it can carry the photocatalyst without compressing the substrate, and particularly when used for masks and filters, the effect on pressure loss is small. Specific examples of the spray dyeing method include a rotor damping method.
得られた光触媒シートを予めＵＶ照射することにより、光触媒の活性をさらに高めることができ、これによりウイルス不活化効果及びウイルス吸着効果がさらに向上する。特にウイルス吸着効果の向上が顕著である。ＵＶ照射により光触媒シートの比表面積が大きくなることが判明し、ＵＶ照射前に比べ１．５倍〜３倍の比表面積の増加が観測された。光触媒加工剤に含まれている分散剤などの添加成分、表面修飾したシリカ化合物の置換基の一部などが光触媒の有機物分解効果により除かれることにより、ウイルスのエンベロープ部が吸着されやすい構造になるものと推定される。ＵＶ照射処理としては、光触媒の付着量や担持する不織布の構成、ＵＶの強度にもよるが、光触媒シート面に太陽光、ブラックライト、殺菌灯などの３４０〜３８０ｎｍ波長を有する光源下で３〜２４時間程度、ＵＶ積算光量として５Ｊ〜４０Ｊ照射すれば効果の向上が発現できる。 By irradiating the obtained photocatalyst sheet with UV in advance, the activity of the photocatalyst can be further increased, and thereby the virus inactivation effect and the virus adsorption effect are further improved. In particular, the improvement of the virus adsorption effect is remarkable. It was found that the specific surface area of the photocatalyst sheet was increased by UV irradiation, and an increase in specific surface area of 1.5 to 3 times that before UV irradiation was observed. Additive components such as dispersants contained in the photocatalyst processing agent and some of the substituents of the surface-modified silica compound are removed by the organic matter decomposition effect of the photocatalyst, so that the structure of the virus envelope is easily adsorbed Estimated. As the UV irradiation treatment, although depending on the amount of photocatalyst attached, the structure of the nonwoven fabric to be supported, and the intensity of UV, the photocatalyst sheet has a light source having a wavelength of 340 to 380 nm such as sunlight, black light, germicidal lamp, etc. The effect can be improved by irradiating 5J to 40J as the UV integrated light amount for about 24 hours.
光触媒シートを予めＵＶ照射する際、メタルハライドランプのような高照度ＵＶを使用することにより、照射時間を大幅に短縮することができ工業的な生産が可能となる。この場合５０ｍＷ〜２５０ｍＷの最大ＵＶ強度を有する光源下、１〜１０分間照射することにより、ブラックライト照射時と同様の効果を得ることができる。高強度ＵＶを光源に用いる場合には、光触媒シートが水に濡れている方が効率よく安定的に比表面積を増大することができる。これはヒドロキシラジカルの原料である水が潤沢に存在することと、高強度ＵＶが発生する熱による不織布基材の損傷が防御できることに起因する。このことから、高強度ＵＶ処理を工業生産的に行う場合には光触媒塗工後、乾燥工程前にＵＶ照射処理をすることがエネルギー効率面で好ましい。 When UV irradiation is performed on the photocatalyst sheet in advance, by using high illuminance UV such as a metal halide lamp, the irradiation time can be greatly shortened and industrial production becomes possible. In this case, by irradiating for 1 to 10 minutes under a light source having a maximum UV intensity of 50 mW to 250 mW, the same effect as that during black light irradiation can be obtained. When high-intensity UV is used as a light source, the specific surface area can be increased efficiently and stably when the photocatalyst sheet is wet with water. This is due to the presence of abundant water, which is a raw material for hydroxy radicals, and the ability to prevent damage to the nonwoven fabric substrate due to the heat generated by high-intensity UV. For this reason, when high-intensity UV treatment is carried out industrially, it is preferable in terms of energy efficiency to perform UV irradiation treatment after the photocatalyst coating and before the drying step.
光触媒シートの比表面積は、概ね光触媒の担持量に比例するが、基材の比表面積や形状の影響を受ける。比表面積が小さい基材に、多量の光触媒を担持させてもあまり有効ではなく、比表面積の大きい基材に薄く均一に担持させることが比表面積の増加に有効である。比表面積が増加すればウイルス吸着能力が向上する。光触媒効果を有効に発揮できる光触媒シートの比表面積は２〜２０m2/ｇであり、好ましくは５〜２０ｍ２／ｇである。２ｍ２/ｇ以下ではウイルス吸着機能が不足すると考えられ、２０ｍ２/ｇ以上は光触媒を多量に担持させる必用があるうえ、光触媒層が厚くなることによりＵＶ照射時間が長くなり、比表面積の効果的な増量にはつながらず、有効ではない。 The specific surface area of the photocatalyst sheet is generally proportional to the amount of photocatalyst supported, but is affected by the specific surface area and shape of the substrate. It is not very effective to carry a large amount of photocatalyst on a substrate having a small specific surface area, and it is effective to increase the specific surface area by carrying it thinly and uniformly on a substrate having a large specific surface area. If the specific surface area is increased, the virus adsorption capacity is improved. The specific surface area of the photocatalyst sheet capable of effectively exhibiting the photocatalytic effect is 2 to 20 m 2 / g, preferably 5 to 20 m 2 / g. It is considered that the virus adsorption function is insufficient at 2 m 2 / g or less, and it is necessary to carry a large amount of photocatalyst at 20 m 2 / g or more, and the UV irradiation time becomes longer due to the thick photocatalyst layer. It is not effective because it does not lead to a regular increase.
本発明の光触媒は、基材を予めアクリル樹脂加工しておくと水洗浄しても光触媒が脱落しない。水耐久性が要求される用途では、基材を予めアクリル樹脂加工しておくことが好ましい。 In the photocatalyst of the present invention, when the substrate is previously processed with an acrylic resin, the photocatalyst does not fall off even when washed with water. In applications where water durability is required, it is preferable that the base material is previously processed with an acrylic resin.
本発明の光触媒シートは、マスクをはじめ、衛生材料、防護服、手袋、ヘアキャップなどのメディカル用途、患者隔離カーテン、インフルエンザパンデミック時の簡易診察用テント、いすカバー、感染者用シーツ、布団カバー、枕カバー、などに使用できる。使用済みのカバーは太陽光やブラックライトなどを照射することにより、さらに感染リスクを低減することができる。
また、本発明の光触媒シートは、空気清浄機、空調用フィルターなどに搭載することができる。この場合は装置内にブラックライトを搭載することにより、有効にウイルスを不活化することができる。
The photocatalytic sheet of the present invention includes masks, sanitary materials, protective clothing, gloves, hair caps and other medical uses, patient isolation curtains, tents for simple diagnosis during influenza pandemics, chair covers, sheets for infected people, futon covers, Can be used for pillow covers, etc. The used cover can further reduce the risk of infection by irradiating it with sunlight or black light.
Moreover, the photocatalyst sheet of this invention can be mounted in an air cleaner, a filter for air conditioning, etc. In this case, the virus can be inactivated effectively by mounting a black light in the apparatus.
本発明の光触媒シートは、ウイルス不活化効果に加え、インフルエンザウイルスに代表されるエンベロープをもつウイルスに対し高い吸着性が得られることからウイルス感染防止マスクの部材として使用することができる。
以下、本発明の光触媒シートを用いてマスクを構成する場合の構成について、詳細に説明する。
本発明の光触媒シートをマスク用途に用いる場合には、不織布の目付は、圧損が大きくならないようにするため１０〜７０ｇ／ｍ２であることが好ましく、より好ましくは１０〜４０ｇ／ｍ２である。目付１０ｇ／ｍ２未満ではインフルエンザウイルス吸着のために十分な比表面積が得られず、７０ｇ／m2を越えると圧損が高くなりすぎる傾向がある。
The photocatalyst sheet of the present invention can be used as a member for a virus infection prevention mask because it has high adsorbability for viruses having an envelope typified by influenza virus in addition to the virus inactivation effect.
Hereafter, the structure in the case of comprising a mask using the photocatalyst sheet of this invention is demonstrated in detail.
In the case of using a photocatalyst sheet of the present invention to mask applications, the basis weight of the nonwoven fabric is preferably 10~70g / m 2 so that the pressure loss does not increase, and more preferably is 10 to 40 g / m 2 . If the basis weight is less than 10 g / m 2 , a sufficient specific surface area cannot be obtained for adsorbing influenza virus, and if it exceeds 70 g / m 2 , the pressure loss tends to be too high.
本発明のマスクは、他者からの感染予防に使用するマスク（以下、感染予防用マスクともいう。）、及び他者への感染を防ぐ患者用に適したマスク（以下、患者用マスクともいう）の両者に使用することができ、本発明の光触媒シートをマスク本体のどの位置に配置するかによりマスクの構成が異なる。
他者からの感染の予防に使用するマスク（感染予防用マスク）については、ウイルス吸着性を有する光触媒を担持したシートを最外層に配置し、ウイルスを含む飛沫を捕捉、吸着する性能が必要であるため、光触媒シートを構成する不織布は極細繊維層を有するものを選択することが、ウイルスの捕捉性が向上するため好ましい。この場合ウイルスの吸着性かつ光による不活化効果を併せ持つ機能が有用であり、昼間屋外での使用や窓がある室内での使用において、エンベロープを有するウイルスに限らず不活化効果が得られるほか、ＵＶ殺菌灯下、太陽光下に暴露することでマスクを手で触れることによる感染リスクを低減することができる。
The mask of the present invention is a mask used for preventing infection from others (hereinafter also referred to as an infection prevention mask) and a mask suitable for a patient that prevents infection to others (hereinafter also referred to as a patient mask). ), And the configuration of the mask differs depending on the position of the photocatalyst sheet of the present invention on the mask body.
For masks used to prevent infection from others (infection prevention masks), a sheet carrying a photocatalyst with virus adsorption is placed on the outermost layer, and the ability to capture and adsorb droplets containing viruses is required. For this reason, it is preferable to select a non-woven fabric constituting the photocatalyst sheet having an ultrafine fiber layer because virus capturing properties are improved. In this case, the function of having both virus adsorptive and light inactivation effects is useful, and in addition to viruses with envelopes, inactivation effects can be obtained when used outdoors in the daytime or indoors with windows, Exposure to UV germicidal lamps and sunlight can reduce the risk of infection by touching the mask with your hand.
極細繊維層を含む不織布は、繊維表面の比表面積が大きくなるため、粒径が小さく、凝集し難い本発明に係る光触媒を、不織布の開孔部を塞ぐことなく繊維表面に担持させることができ、より有効に光触媒の効果を発揮できる。熱可塑性繊維からなるＳＭＭＳ、ＳＭＳ又はＳＭ不織布の場合のスパンボンド層の繊維径は７〜２０μｍであることが好ましく、メルトブロウン層の繊維径は０．５〜５．０μｍが好ましく、より好ましくは１．５〜３．０μｍである。メルトブロウン層の繊維径が０．５μｍ以下の場合は緻密になりすぎ圧力損失が大きくなる。また、ＳＭＳ又はＳＭ不織布のメルトブロウン層が構成する部分の目付けとしては、１ｇ／ｍ２〜２０ｇ／ｍ２が好ましく、より好ましくは１ｇ／ｍ２〜１５ｇ／ｍ２である。 Since the nonwoven fabric containing the ultrafine fiber layer has a large specific surface area on the fiber surface, the photocatalyst according to the present invention, which has a small particle size and is difficult to agglomerate, can be supported on the fiber surface without blocking the openings of the nonwoven fabric. Thus, the effect of the photocatalyst can be exhibited more effectively. In the case of SMMS, SMS or SM nonwoven fabric made of thermoplastic fibers, the fiber diameter of the spunbond layer is preferably 7 to 20 μm, and the fiber diameter of the meltblown layer is preferably 0.5 to 5.0 μm, more preferably 1.5 to 3.0 μm. When the fiber diameter of the meltblown layer is 0.5 μm or less, it becomes too dense and the pressure loss increases. As the basis weight of the portion meltblown layer of SMS or SM nonwoven fabric constitutes, preferably 1g / m 2 ~20g / m 2 , more preferably from 1g / m 2 ~15g / m 2 .
本発明の感染予防用マスクの中間層としては、飛沫の水分が蒸発し、飛沫核化したウイルスの侵入を防ぐため、捕集性能が高い帯電加工処理をしたメルトブロウン不織布を光触媒より内側の中間層として使用することが好ましい。不織布の目付としては、１０〜４０ｇ／ｍ２のシートを単数又は複数枚使用することができる。帯電加工処理をしたメルトブロウン不織布はポリプロピレンメルトブロウン不織布がより好ましい。本発明のマスクの口元層を構成する不織布は、肌と直接触れる部分であり、風合いが柔らかく毛羽が発生しにくい不織布が好ましい。使用例としては長繊維不織布が好ましく、ポリプロピレンスパンボンド、ナイロンスパンボンド、ポリエステル系スパンボンド、セルロース長繊維不織布が挙げられる。とくに圧力損失が損なわれない範囲で選択することができる。
このように感染予防用マスクは、光触媒シートを最外層に、帯電加工されたポリプロピレンメルトブロウン不織布を中間層に、口元層には肌触りの良い長繊維不織布の少なくとも３層から構成される。中間層には圧損が高くなり過ぎない範囲で更なる機能性シート、支持体シートなど、帯電加工されたシートなど積層しても差し支えない。
As an intermediate layer of the infection prevention mask of the present invention, a melt-blown non-woven fabric subjected to electrification processing having a high collection performance is used as an intermediate layer inside the photocatalyst in order to prevent the intrusion of the splashed nucleated virus due to evaporation of the splashed water. It is preferable to use it as a layer. As a fabric weight of a nonwoven fabric, the sheet | seat of 10-40 g / m < 2 > can use single or multiple sheets. The melt-blown nonwoven fabric subjected to the charging process is more preferably a polypropylene melt-blown nonwoven fabric. The non-woven fabric constituting the mouth layer of the mask of the present invention is preferably a non-woven fabric that is in direct contact with the skin and has a soft texture and hardly generates fluff. As a use example, a long fiber nonwoven fabric is preferable, and a polypropylene spunbond, a nylon spunbond, a polyester spunbond, and a cellulose long fiber nonwoven fabric are mentioned. In particular, it can be selected within a range where the pressure loss is not impaired.
Thus, the infection prevention mask is composed of at least three layers of a long-fiber non-woven fabric that is soft to the mouth layer and a photo-catalytic sheet as an outermost layer, a charged polypropylene melt-blown non-woven fabric as an intermediate layer, and a mouth layer. The intermediate layer may be laminated with a charged sheet such as a functional sheet or a support sheet as long as the pressure loss does not become too high.
他者への感染を防ぐ患者用に適したマスク（患者用マスク）については、口元層に近い中間層に本発明の光触媒シートを配置することが有効である。特にウイルスを含む飛沫を捕捉する効果が高い帯電加工したポリプロピレンメルトブロウン不織布と隣接し、且つ口元側に光触媒シートを配置するのが好ましい。この用途に用いる光触媒シートは圧損が高くならない範囲で繊維量が多く光触媒の担持量が多い方が好ましい。 For a mask suitable for a patient that prevents infection to others (patient mask), it is effective to arrange the photocatalytic sheet of the present invention in an intermediate layer close to the mouth layer. In particular, it is preferable to dispose a photocatalyst sheet adjacent to the electrically charged polypropylene meltblown nonwoven fabric having a high effect of capturing the virus-containing droplets and on the mouth side. It is preferable that the photocatalyst sheet used for this purpose has a large amount of fibers and a large amount of photocatalyst supported within a range where pressure loss does not increase.
光触媒を担持させる基材としては、セルロース繊維も好ましく用いられる。セルロース繊維は水分率が高いため、光触媒の有機物分解効果が高くなり好ましい。セルロース繊維不織布の例としては長繊維不織布、スパンレース不織布などが挙げられる。セルロース繊維は親水性が高く、ウイルスを含む飛沫の吸着性が高いため、とくに患者用マスク用途の内層に用いる光触媒シート基材に使用するのに有効である。この場合光触媒シートと接し、光触媒シートの外側に位置する帯電加工されたメルトブロウン不織布により飛沫がブロックされ、光触媒シートに吸収されることにより、飛沫に含まれるウイルスが担持した光触媒に吸着され乾燥後も飛散しないため、より効果的に感染患者からの咳・くしゃみによるウイルスの飛散を防御することができる。特に、インフルエンザウイルスの吸着性能が重要な患者用マスクの中間層に用いる場合には１〜５ｇ／ｍ２の担持が好ましい。 Cellulose fibers are also preferably used as the substrate for supporting the photocatalyst. Cellulose fibers are preferred because they have a high moisture content, and thus the organic matter decomposition effect of the photocatalyst increases. Examples of the cellulose fiber nonwoven fabric include long fiber nonwoven fabric and spunlace nonwoven fabric. Cellulose fibers are highly hydrophilic and highly adsorbable for droplets containing viruses, and are therefore particularly effective for use as a photocatalytic sheet base material used as an inner layer for patient mask applications. In this case, the droplets are blocked by the charged melt-blown nonwoven fabric that is in contact with the photocatalyst sheet and located outside the photocatalyst sheet, and absorbed by the photocatalyst sheet, so that the virus contained in the droplets is adsorbed by the photocatalyst and dried. Therefore, the virus can be more effectively prevented from being scattered by coughing and sneezing from an infected patient. In particular, when it is used for an intermediate layer of a patient mask in which the ability to adsorb influenza virus is important, loading of 1 to 5 g / m 2 is preferable.
以上のように患者用マスクについては、最外層に毛羽が出にくい長繊維不織布、中間層外層側には帯電加工されたポリプロピレンメルトブロウン不織布、中間層内層側には光触媒シート、口元層には上記肌触りの良い長繊維不織布の少なくとも４層が好ましい使用例となる。 As described above, for the patient mask, the long-fiber nonwoven fabric in which the outermost layer is less prone to fluff, the intermediate layer outer layer side is a charged polypropylene meltblown nonwoven fabric, the intermediate layer inner layer side is a photocatalyst sheet, and the mouth layer is the above At least four layers of a long-fiber non-woven fabric having a good touch is a preferred use example.
耳掛け部に使用する伸縮性シートや伸縮テープ、ゴムひもなども該光触媒を加工しておくとより安全性が向上する。
本発明のマスクは、顔面の一部を覆うハーフマスクであり、その形状は、折りたたみ型、カップ型又はフラット型のいずれでもよい。
If the photocatalyst is processed for an elastic sheet, an elastic tape, a rubber string, or the like used for the ear hook, the safety is further improved.
The mask of the present invention is a half mask that covers a part of the face, and the shape may be any of a folding type, a cup type, and a flat type.
以下、本発明を実施例により具体的に説明する。
以下の方法により、本発明に係る光触媒を製造した。
［光触媒製造方法］
還流冷却器、温度計、及び攪拌装置を取り付けた反応器に、ジオキサン５００ｇと、ＫＦ９９０１｛メチルハイドロジェンシロキサンージメチルシロキサンコポリマーの商品名（信越化学製）、Ｓｉ−Ｈ基含有７．１４ｍｍｏｌ／ｇ（カタログ記載値）、重量平均分子量３９００｝５００ｇを入れ、攪拌下８０℃に昇温した。これにユニオックスＭＵＳ−８｛ポリオキシエチレンアリルメチルエーテルの商品名（日本油脂製）、重量平均分子量８００（カタログ記載値）｝１３７０ｇと塩化白金（ＩＶ）酸六水和物の５重量％イソプロパノール溶液５ｇをジオキサン２３１０ｇに溶解した溶液を、８０℃にて攪拌下約１時間かけて添加し、さらに８０℃にて２時間攪拌を続けた後、室温にまで冷却することにより、Ｓｉ−Ｈ基含有ケイ素化合物（１）｛以下、化合物（１）という。｝を含む溶液を得た。
Hereinafter, the present invention will be specifically described by way of examples.
The photocatalyst according to the present invention was produced by the following method.
[Photocatalyst production method]
In a reactor equipped with a reflux condenser, a thermometer, and a stirrer, 500 g of dioxane, KF9901 {trade name of methylhydrogensiloxane-dimethylsiloxane copolymer (manufactured by Shin-Etsu Chemical), Si-H group-containing 7.14 mmol / g (Catalog value), weight average molecular weight 3900} 500 g was added, and the temperature was raised to 80 ° C. with stirring. UNIOX MUS-8 {trade name of polyoxyethylene allyl methyl ether (manufactured by NOF Corporation), weight average molecular weight 800 (catalog value)} 1370 g and 5% by weight isopropanol of platinum chloride (IV) acid hexahydrate A solution prepared by dissolving 5 g of the solution in 2310 g of dioxane was added at 80 ° C. over about 1 hour with stirring, and further stirred at 80 ° C. for 2 hours. Containing silicon compound (1) {hereinafter referred to as compound (1). } Was obtained.
還流冷却器、温度計、及び攪拌装置を取り付けた反応器に、ＴＯ−２４０｛粒子表面がペルオキソ基で修飾されたアナターゼ型酸化チタンを含有するゾルの商品名（田中転写製）、ゾル中に分散した粒子の体積平均粒子径１５ｎｍ、ＴｉＯ２濃度２．４重量％｝４２０ｇを入れ、これに化合物（１）を含む溶液２３．４ｇを３０℃にて攪拌下約３０分かけて添加し、さらに３０℃にて１０時間攪拌を続けることにより、非常に分散性の良好な、体積平均粒子径１７ｎｍの変性酸化チタン粒子を含有する光触媒水分散体（２）を得た。 In a reactor equipped with a reflux condenser, a thermometer, and a stirring device, TO-240 {trade name of sol containing anatase-type titanium oxide whose particle surface is modified with a peroxo group (manufactured by Tanaka Transcription Co., Ltd.) 420 g of a volume average particle diameter of dispersed particles of 15 nm, a TiO 2 concentration of 2.4 wt%} is added, and 23.4 g of a solution containing the compound (1) is added thereto at 30 ° C. with stirring over about 30 minutes. Furthermore, by continuing stirring at 30 ° C. for 10 hours, a photocatalyst water dispersion (2) containing modified titanium oxide particles having a very good dispersibility and a volume average particle diameter of 17 nm was obtained.
本発明に係る光触媒シート、及びマスクの特性を以下の方法で測定した。尚、ウイルス吸着性能については、国立感染症研究所との共同研究により実施した、以下の実施例１と２、比較例１と２についての評価を、以下の表１に示す。 The characteristics of the photocatalyst sheet according to the present invention and the mask were measured by the following method. In addition, about the virus adsorption | suction performance, evaluation about the following Examples 1 and 2 and the comparative examples 1 and 2 which were implemented by joint research with the National Institute of Infectious Diseases is shown in Table 1 below.
［ウイルス吸着効果試験］
本試験は国立感染症研究所バイオセーフティ管理室との共同研究で実施した。予めＵＶ照射した光触媒シートをイオン交換水で洗浄した後、縦横１ｃｍ×１ｃｍの試験片に裁断し、２０ＫＧｙの電子線を照射し滅菌した。
１ｃm2の各試験片を１２well plateの各well内に置く。ここに各ウイルス液１０μL滴下し、室温で所定時間静置する。その後各ウイルス培養培地を０．５mL/well加え、攪拌してウイルスを溶出させる。この溶出液を培地にて５倍段階希釈し、各培養細胞単層９６well-plateに接種し、３〜７日間培養した後、１０％ホルマリン液固定、メチレンブルー染色を行い、５０％感染価（ＴＣＩＤ50）を算出した。
[Virus adsorption effect test]
This study was conducted in collaboration with the National Institute of Infectious Diseases Biosafety Management Office. The photocatalyst sheet previously irradiated with UV was washed with ion-exchanged water, then cut into 1 cm × 1 cm test pieces in length and width, and sterilized by irradiation with 20 KGy electron beams.
Place each test piece of 1 cm 2 in each well of a 12 well plate. Here, 10 μL of each virus solution is dropped and left at room temperature for a predetermined time. Thereafter, 0.5 mL / well of each virus culture medium is added and stirred to elute the virus. This eluate was diluted 5-fold with culture medium, inoculated into each culture cell monolayer 96 well-plate, cultured for 3 to 7 days, fixed with 10% formalin solution, stained with methylene blue, and 50% infectivity titer (TCID). 50 ) was calculated.
供試ウイルスは、以下の：
インフルエンザＡウイルス（Ｈ１Ｎ１）型 ニューカレドニア株
インフルエンザＡウイルス（Ｈ３Ｎ２）型 パナマ株
インフルエンザＢウイルス
ネコカリシウイルス（ＦＣＶ）
ヒトアデノウイルス ｔｙｐｅ―３（ＨＡｄＶ−３）
であった。
また、培養液は、以下の：
インフルエンザ：０．３％ＢＳＡ−Ｅａｇｌｅ‘ＭＥＭ
ＦＣＶとＨＡｄＶ：５％ＢＳＡ−Ｅａｇｌｅ‘ＭＥＭ
であった。
The test viruses are as follows:
Influenza A virus (H1N1) type New Caledonia strain Influenza A virus (H3N2) type Panama strain Influenza B virus feline calicivirus (FCV)
Human adenovirus type-3 (HAdV-3)
Met.
In addition, the culture solution is as follows:
Influenza: 0.3% BSA-Eagle'MEM
FCV and HAdV: 5% BSA-Eagle'MEM
Met.
［ウイルス不活化効果試験］
本試験は国立感染症研究所バイオセーフティ管理室との共同研究で実施した。予めＵＶ照射した光触媒シートをイオン交換水で洗浄した後、縦横１ｃｍ×１ｃｍの試験片に裁断し、２０ＫＧｙの電子線を照射し滅菌した。
１ｃm2の各試験片を１２well plateの各well内に置く。ここに各ウイルス液１０μL滴下し、室温で５分静置する。ここにＵＶ−Ａを１２００−１４００μＷ・ｃｍで照射し、一定時間ごとに試験片を回収する。回収後、直ちに各ウイルス培養培地を０．５mLで溶出し、これを５倍段階希釈したものを各培養細胞単層９６well-plateに接種し、３〜７日間培養した後、１０％ホルマリン液固定、メチレンブルー染色を行い、５０％感染価（ＴＣＩＤ50）を算出した。
試験ウイルス及び培養液として、前記したウイルス吸着効果試験に供したものと同じものを使用した。
[Virus inactivation effect test]
This study was conducted in collaboration with the National Institute of Infectious Diseases Biosafety Management Office. The photocatalyst sheet previously irradiated with UV was washed with ion-exchanged water, then cut into 1 cm × 1 cm test pieces in length and width, and sterilized by irradiation with 20 KGy electron beams.
Place each test piece of 1 cm 2 in each well of a 12 well plate. To this, 10 μL of each virus solution is dropped and allowed to stand at room temperature for 5 minutes. Here, UV-A is irradiated at 1200 to 1400 μW · cm, and test pieces are collected at regular intervals. Immediately after the collection, each virus culture medium was eluted with 0.5 mL, and a 5-fold serial dilution was inoculated into each cultured cell monolayer 96 well-plate, cultured for 3-7 days, and then fixed with 10% formalin solution. Then, methylene blue staining was performed, and the 50% infectivity titer (TCID 50 ) was calculated.
The same test virus and culture solution as those used for the virus adsorption effect test described above were used.
［比表面積（ｍ２／ｇ）の測定方法］
自動比表面積測定装置（ジェミニ２３６０：島津製作所製）を用い、ＢＥＴ多点法により測定した。吸着ガスとしては、純度９９．９９％の窒素ガスを用いた。
[Measurement method of specific surface area (m 2 / g)]
It measured by the BET multipoint method using the automatic specific surface area measuring apparatus (Gemini 2360: Shimadzu Corporation make). Nitrogen gas with a purity of 99.99% was used as the adsorption gas.
［目付(ｇ／ｍ２)］
縦25cm×横25cmの試料を３カ所切り取り、重量を測定し、その平均値を質量に換算して求めた。JIS-L-1906に準拠した。
[Weight per unit (g / m 2 )]
Three samples measuring 25 cm long × 25 cm wide were cut out, weighed, and the average value was converted to mass. Conforms to JIS-L-1906.
［厚み(μm)］
JIS-L-1906に準拠した。
[Thickness (μm)]
Conforms to JIS-L-1906.
［光触媒の吸着能力（アンモニア吸着効果、光触媒吸着効果）］
光触媒シート又はマスクの一部を５ｃｍ×１０ｃｍに切り出して、１Ｌのテドラバッグに入れ、アンモニアガス（２００ｐｐｍ）を６００ｍＬ封入する。２０℃に設定したインキュベーター内暗所で３０分安置後、検知管にてアンモニア濃度を測定した。残留アンモニア濃度より、光触媒の吸着能力を判定した。
尚、以下の表３中、アンモニア吸着効果を、効果の高い順に、◎、○、△、×で格付けした。また、以下の表４中、光触媒吸着効果を、効果の高い順に、◎、○、△、×で格付けした。
[Adsorption capacity of photocatalyst (ammonia adsorption effect, photocatalyst adsorption effect)]
A part of the photocatalyst sheet or mask is cut into 5 cm × 10 cm, put into a 1 L tedlar bag, and 600 mL of ammonia gas (200 ppm) is sealed. After standing for 30 minutes in a dark place in an incubator set at 20 ° C., the ammonia concentration was measured with a detector tube. The adsorption ability of the photocatalyst was determined from the residual ammonia concentration.
In Table 3 below, the ammonia adsorption effect was rated by ◎, ○, Δ, × in descending order of effect. In Table 4 below, the photocatalyst adsorption effect was rated by ◎, ○, Δ, × in descending order of effect.
［光触媒の有機物分解能力（効果）］
光触媒シート又はマスクの一部を５ｃｍ×１０ｃｍに切り出して、１Ｌのテドラバッグに入れ、アンモニアガス（２００ｐｐｍ）を６００ｍＬ封入する。２０℃に設定したインキュベーター内でブラックライトを０．６ｍＷ／ｃｍ２の照射強度になるように照射位置を調節し、３０分安置後、検知管にてアンモニア濃度を測定した。残留アンモニア濃度より、光触媒の有機物分解能力を判定した。
尚、以下の表４中、光触媒有機物分解効果を、効果の高い順に、◎、○、△、×で格付けした。また、以下の表３中、アンモニア消臭試験における有機物分解効果を、効果の高い順に、◎、○、△、×で格付けした。
[Photocatalyst's ability to decompose organic substances (effect)]
A part of the photocatalyst sheet or mask is cut into 5 cm × 10 cm, put into a 1 L tedlar bag, and 600 mL of ammonia gas (200 ppm) is sealed. The irradiation position was adjusted so that the irradiation intensity of the black light was 0.6 mW / cm 2 in an incubator set at 20 ° C., and the ammonia concentration was measured with a detector tube after being placed for 30 minutes. The ability of the photocatalyst to decompose organic matter was determined from the residual ammonia concentration.
In Table 4 below, the photocatalytic organic matter decomposition effects were rated by ◎, ○, Δ, × in descending order of effectiveness. Moreover, in the following Table 3, the organic substance decomposition effect in the ammonia deodorization test was rated by ◎, ○, Δ, × in descending order of effect.
［実施例１］
プレシゼＡ１２９０（旭化成せんい製）にアクリル樹脂ボンコートＲ３３８０−Ｅ（大日本インキ社製）５％ｓoｌ.をＤｉｐ−Ｎｉｐにて塗工し、１５０℃×６０秒間、乾熱処理を行った。さらに上記光触媒水分散体（２）固形分５％溶液をＤｉｐ−Ｎｉｐにて塗工し、光触媒４ｇ／ｍ２を担持したシートを作製した。このシートをイオン交換水で洗浄して乾燥した後、０．５ｍＷ／cm2のＵＶ強度を持つブラックライトを表裏各２４時間照射した。得られた光触媒シートの Ｔｉ成分のＸ線強度は８７．９ｋｃｐｓであった。
[Example 1]
5% sol. Of acrylic resin Boncoat R3380-E (Dainippon Ink Co., Ltd.) was applied to Presise A1290 (manufactured by Asahi Kasei Fiber) with Dip-Nip, and dry heat treatment was performed at 150 ° C. for 60 seconds. Further coating the photocatalyst aqueous dispersion (2) a 5% solids solution at Dip-Nip, and the photocatalyst 4g / m 2 to prepare a carrying sheet. The sheet was washed with ion-exchanged water and dried, and then irradiated with black light having a UV intensity of 0.5 mW / cm 2 for 24 hours on both sides. The X-ray intensity of the Ti component of the obtained photocatalyst sheet was 87.9 kcps.
[実施例２]
プレシゼＡ１２９０（旭化成せんい製）にアクリル樹脂ボンコートＲ３３８０−Ｅ ５％ｓoｌ.をＤｉｐ−Ｎｉｐにて塗工し、１５０℃×６０秒間、乾熱処理を行った。さらに上記光触媒水分散体（２）固形分０．５％溶液をＤｉｐ−Ｎｉｐにて塗工し、光触媒０．４ｇ／ｍ２を担持したシートを作製した。このシートをイオン交換水で洗浄して乾燥した後、０．５ｍＷ／ｃｍ２のＵＶ強度を持つブラックライトを表裏各２４時間照射した。得られた光触媒シートの Ｔｉ成分のＸ線強度は１２．５ｋｃｐｓであった。
[Example 2]
Acrylic resin bon coat R3380-E 5% sol. Was applied to Presise A1290 (manufactured by Asahi Kasei Fibers) with Dip-Nip and subjected to a dry heat treatment at 150 ° C. for 60 seconds. Furthermore, the photocatalyst water dispersion (2) 0.5% solid content solution was coated with Dip-Nip to prepare a sheet carrying 0.4 g / m 2 of the photocatalyst. The sheet was washed with ion-exchanged water and dried, and then irradiated with black light having a UV intensity of 0.5 mW / cm 2 for 24 hours on both sides. The X-ray intensity of the Ti component of the obtained photocatalyst sheet was 12.5 kcps.
[実施例３]
プレシゼＡ１２９０（旭化成せんい製）にアクリル樹脂ボンコートＲ３３８０−Ｅ ５％ｓoｌ.をＤｉｐ−Ｎｉｐにて塗工し、１５０℃×６０秒間、乾熱処理を行った。さらに上記光触媒水分散体（２）固形分１．２％溶液をＤｉｐ−Ｎｉｐにて塗工し、光触媒１ｇ／ｍ２を担持したシートを作製した。このシートをイオン交換水で洗浄して乾燥した後、０．５ｍＷ／ｃｍ２のＵＶ強度を持つブラックライトを表裏各２４時間照射した。得られた光触媒シートの Ｔｉ成分のＸ線強度は２４．５ｋｃｐｓであった。
[Example 3]
Acrylic resin bon coat R3380-E 5% sol. Was applied to Presise A1290 (manufactured by Asahi Kasei Fibers) with Dip-Nip and subjected to a dry heat treatment at 150 ° C. for 60 seconds. Furthermore, the photocatalyst water dispersion (2) 1.2% solid content solution was coated with Dip-Nip to prepare a sheet carrying 1 g / m 2 of photocatalyst. The sheet was washed with ion-exchanged water and dried, and then irradiated with black light having a UV intensity of 0.5 mW / cm 2 for 24 hours on both sides. The X-ray intensity of the Ti component of the obtained photocatalyst sheet was 24.5 kcps.
[実施例４]
プレシゼＡ１２９０（旭化成せんい製）にアクリル樹脂ボンコートＲ３３８０−Ｅ ５％ｓoｌ.をＤｉｐ−Ｎｉｐにて塗工し、１５０℃×６０秒間、乾熱処理を行った。さらに上記光触媒水分散体（２）固形分２．５％溶液をＤｉｐ−Ｎｉｐにて塗工し、光触媒２ｇ／ｍ２を担持したシートを作製した。このシートをイオン交換水で洗浄して乾燥した後、０．５ｍＷ／ｃｍ２のＵＶ強度を持つブラックライトを表裏各２４時間照射した。得られた光触媒シートの Ｔｉ成分のＸ線強度は４４．９ｋｃｐｓであった。
[Example 4]
Acrylic resin bon coat R3380-E 5% sol. Was applied to Presise A1290 (manufactured by Asahi Kasei Fibers) with Dip-Nip and subjected to a dry heat treatment at 150 ° C. for 60 seconds. Further coating the photocatalyst aqueous dispersion (2) solid content of 2.5% solution at Dip-Nip, and the photocatalyst 2 g / m 2 to prepare a carrying sheet. The sheet was washed with ion-exchanged water and dried, and then irradiated with black light having a UV intensity of 0.5 mW / cm 2 for 24 hours on both sides. The X-ray intensity of the Ti component of the obtained photocatalyst sheet was 44.9 kcps.
[参考例５]
エルタスＮ０１０７０（旭化成せんい製）に上記光触媒水分散体（２）固形分２．５％溶液をＤｉｐ−Ｎｉｐにて塗工し、光触媒２ｇ／ｍ２担持したシートを作製した。このシートを０．５ｍＷ／ｃｍ２のＵＶ強度を持つブラックライトを表裏各２４時間照射した。得られた光触媒シートの Ｔｉ成分のＸ線強度は３０．２ｋｃｐｓであった。
[ Reference Example 5]
The above-mentioned photocatalyst aqueous dispersion (2) 2.5% solid content solution was applied to Eltus N01070 (manufactured by Asahi Kasei Fibers) with Dip-Nip to produce a sheet carrying 2 g / m 2 of photocatalyst. This sheet was irradiated with black light having a UV intensity of 0.5 mW / cm 2 for 24 hours on the front and back sides. The X-ray intensity of the Ti component of the obtained photocatalyst sheet was 30.2 kcps.
[実施例６]
エルタスＰＭＡ０４０（ＳＭＭＳ；旭化成せんい製）にアクリル樹脂ボンコートＲ３３８０−Ｅ ５％ｓoｌ.をＤｉｐ−Ｎｉｐにて塗工し、１５０℃×６０秒間、乾熱処理を行った。さらに上記光触媒水分散体（２）固形分３％溶液をＤｉｐ−Ｎｉｐにて塗工し、光触媒２ｇ／ｍ２を担持したシートを作製した。このシートをイオン交換水で洗浄して乾燥した後、０．５ｍＷ／ｃｍ２のＵＶ強度を持つブラックライトを表裏各２４時間照射した。得られた光触媒シートの Ｔｉ成分のＸ線強度は２６．５ｋｃｐｓであった。
[Example 6]
Acrylic resin bon coat R3380-E 5% sol. Was applied to Eltus PMA040 (SMMS; manufactured by Asahi Kasei Fibers) with Dip-Nip, followed by dry heat treatment at 150 ° C. for 60 seconds. Further coating the photocatalyst aqueous dispersion (2) 3% solids solution at Dip-Nip, and the photocatalyst 2 g / m 2 to prepare a carrying sheet. The sheet was washed with ion-exchanged water and dried, and then irradiated with black light having a UV intensity of 0.5 mW / cm 2 for 24 hours on both sides. The X-ray intensity of the Ti component of the obtained photocatalyst sheet was 26.5 kcps.
[比較例１]
プレシゼＡ１２９０を縦横１ｃｍ×１ｃｍの試験片に裁断し、２０ＫＧｙの電子線を照射し滅菌した。このシートのＴｉ成分のＸ線強度は４．５ｋｃｐｓであった。このシートをウイルス試験のコントロールとした。
[Comparative Example 1]
Precise A1290 was cut into 1 cm × 1 cm test pieces, and sterilized by irradiation with an electron beam of 20 KGy. The X-ray intensity of the Ti component of this sheet was 4.5 kcps. This sheet served as a virus test control.
[比較例２]
プレシゼＡ１２９０にアクリル樹脂ボンコートＲ３３８０−Ｅ（大日本インキ社製）５％ｓoｌ.をＤｉｐ−Ｎｉｐにて塗工し、１５０℃×６０秒間、乾熱処理を行った。さらにＳＴＳ−０２｛アナターゼ型酸化チタンゾルの商品名（石原産業製）｝酸化チタンゾルを固形分５％溶液に希釈し、Ｄｉｐ−Ｎｉｐにて塗工し、光触媒４ｇ／ｍ２を担持したシートを作製した。 このシートをイオン交換水で洗浄して乾燥した後、０．５ｍＷ／ｃｍ２のＵＶ強度を持つブラックライトを表裏各２４時間照射した。得られた光触媒シートの Ｔｉ成分のＸ線強度は７９ｋｃｐｓであった。
[Comparative Example 2]
Presize A1290 was coated with 5% sol. Of acrylic resin Boncoat R3380-E (Dainippon Ink Co., Ltd.) with Dip-Nip, and was subjected to a dry heat treatment at 150 ° C. for 60 seconds. Further, STS-02 {trade name of anatase type titanium oxide sol (manufactured by Ishihara Sangyo)} Titanium oxide sol is diluted to a 5% solid content solution and coated with Dip-Nip to produce a sheet carrying a photocatalyst 4 g / m 2. did. The sheet was washed with ion-exchanged water and dried, and then irradiated with black light having a UV intensity of 0.5 mW / cm 2 for 24 hours on both sides. The X-ray intensity of the Ti component of the obtained photocatalyst sheet was 79 kcps.
[実施例７]
外層として表面修飾した光触媒を４ｇ／ｍ２担持させたプレシゼＡ１１６０（ポリエステルＳＭＳ不織布；旭化成せんい製）を配置し、中間層としてクラレ社製ポリプルピレンメルトブロウン不織布（帯電加工） ２０ｇ／ｍ２、内層として、旭化成せんい社製 ベンリーゼ １４ｇ／m2を配置し、ヨコ１７ｃｍ、タテ１７ｃｍの不織布を横方向にひだが３列できるように折りたたみ、製品サイズヨコ１７ｃｍ、タテ９ｃｍ、両ヨコに耳掛け用ゴムを配置した折りたたみ型マスクを作製した。
[Example 7]
Precise A1160 (polyester SMS nonwoven fabric; manufactured by Asahi Kasei Fiber) carrying 4 g / m 2 of a surface-modified photocatalyst as an outer layer is disposed, and a polypropylene meltblown nonwoven fabric (charging process) manufactured by Kuraray Co., Ltd. as an intermediate layer is 20 g / m 2 . As the inner layer, Benisese 14g / m 2 manufactured by Asahi Kasei Fibers Co., Ltd. is placed, and a non-woven fabric of 17cm in width and 17cm in length is folded so that it can be folded in three rows horizontally. Product size is horizontal 17cm, vertical 9cm, for both ears A folding mask with rubber was prepared.
[実施例８]
外層として表面修飾した光触媒を１ｇ／ｍ２担持させたプレシゼＡ１１６０（ポリエステルＳＭＳ不織布；旭化成せんい製）を配置し、中間層としてクラレ社製ポリプルピレンメルトブロウン不織布（帯電加工）２０ｇ／ｍ２、内層として、ベンリーゼ（旭化成せんい製） １４ｇ／ｍ２を配置して、参考例５と同様の形状のマスクを作製した。
[Example 8]
Precise A1160 (polyester SMS nonwoven fabric; manufactured by Asahi Kasei Fiber) carrying 1 g / m 2 of a surface-modified photocatalyst as an outer layer is disposed, and a polypropylene meltblown nonwoven fabric (charging process) 20 g / m 2 manufactured by Kuraray Co., Ltd. is used as an intermediate layer. As an inner layer, 14 g / m 2 of Benrise (manufactured by Asahi Kasei Fibers Co., Ltd.) was arranged to produce a mask having the same shape as in Reference Example 5.
[実施例９]
外層として表面修飾した光触媒を１ｇ／ｍ２担持させたＳＭ不織布を配置し、中間層としてクラレ社製ポリプロピレンメルトブロウン不織布（帯電加工） ２０ｇ／ｍ２、内層として、エルタスＰ０３０２０（旭化成せんい製）２０ｇ／ｍ２を配置し、参考例５と同様の形状のマスクを作製した。
光触媒を担持させたＳＭ不織布は、スパンボンドＥ０１０１２（旭化成せんい製）に（目付１２ｇ／ｍ２、平均繊維径２μｍのＰＥＴメルトブロウン繊維を１５ｇ吹き付けながら積層し、ＰＥＴＳＭ構造の不織布を作製した。
[Example 9]
An SM non-woven fabric carrying 1 g / m 2 of a surface-modified photocatalyst as an outer layer is arranged, a polypropylene melt-blown non-woven fabric made by Kuraray Co., Ltd. (charging process) is 20 g / m 2 as an intermediate layer, and 20 g / m 2 as an inner layer. / M 2 was placed, and a mask having the same shape as in Reference Example 5 was produced.
The SM nonwoven fabric carrying the photocatalyst was laminated while spun bond E01012 (manufactured by Asahi Kasei Fibers) with 15 g of PET meltblown fiber having a basis weight of 12 g / m 2 and an average fiber diameter of 2 μm to produce a PETSM structure nonwoven fabric.
[実施例１０]
外層として エルタスＰ０３０２０（スパンボンド；旭化成せんい製） ２０ｇ／ｍ２、中間層１として、クラレ社製ポリプロピレンメルトブロウン不織布（帯電加工）、中間層２として、光触媒を４ｇ／ｍ２担持させたプレシゼＡ１１６０（ポリエステルＳＭＳ不織布；旭化成せんい製）を配置し、内層として旭化成せんい社製 ベンリーゼ １４ｇ／ｍ２を配置し、実施例７と同様の形状のマスクを作製した。
[Example 10]
Ertas P03020 (spunbond; manufactured by Asahi Kasei Fibers) as the outer layer, 20 g / m 2 as the intermediate layer 1, polypropylene meltblown nonwoven fabric (charging process) manufactured by Kuraray Co., Ltd., and Presise A1160 carrying 4 g / m 2 of the photocatalyst as the intermediate layer 2 (Polyester SMS non-woven fabric; manufactured by Asahi Kasei Fiber) was disposed, Benlyse 14 g / m 2 manufactured by Asahi Kasei Fibers Co., Ltd. was disposed as an inner layer, and a mask having the same shape as in Example 7 was produced.
［実施例１１］
外層としてエルタスＰ０３０２０（スパンボンド；旭化成せんい製）２０ｇ／ｍ２、中間層１として、クラレ社製ポリプロピレンメルトブロウン不織布（帯電加工）、中間層２として、光触媒を５ｇ／m2担持させた旭化成社製ベンリーゼ ４０ｇ／ｍ２を配置し、内層としてプレシゼＰＯ１０２０（旭化成せんい製） ２０ｇ／ｍ２を配置し、実施例７と同様の形状のマスクを作製した。
[Example 11]
Eltas as the outer layer P03020 (spunbond; Fibers produced by Asahi Chemical Industry) 20 g / m 2, as an intermediate layer 1, manufactured by Kuraray Co., Ltd. Polypropylene meltblown nonwoven (charging process), as an intermediate layer 2, Asahi Kasei Corporation which the photocatalyst was 5 g / m 2 supported Ltd. Bemliese 40 g / m 2 was placed, the Pureshize PO1020 (manufactured Fibers Asahi Kasei) 20 g / m 2 was placed as an inner layer, to prepare a mask having the same shape as in example 7.
[比較例３]
表層に光触媒を担持しないプレシゼＡ１１６０（ポリエステルＳＭＳ不織布；旭化成せんい製）を用いた以外は、実施例７と同様にして折りたたみ型マスクを成形し、その評価を行った。
[Comparative Example 3]
A foldable mask was molded and evaluated in the same manner as in Example 7 except that Precise A1160 (polyester SMS nonwoven fabric; manufactured by Asahi Kasei Fiber) that did not carry a photocatalyst on the surface layer was used.
[比較例４]
中間層２にとして、光触媒を担持しないベンリーゼ（旭化成せんい製） ４０ｇ／ｍ２を配置した以外は、実施例１１と同様にして折りたたみ型マスクを成形し、その評価を行った。
[Comparative Example 4]
A folding mask was molded and evaluated in the same manner as in Example 11 except that 40 g / m 2 of Benrise (produced by Asahi Kasei Fiber) not supporting a photocatalyst was disposed as the intermediate layer 2.
上記実施例１〜１１、及び比較例１〜４の評価結果を以下の表１〜４に示す。
本発明の光触媒シートは、光触媒のＵＶ光による有機物分解効果から得られるウイルスの不活化効果に加え、インフルエンザウイルスのようなエンベロープを持つウイルスに対しては光の存在しない空間や夜間でも強力な吸着性能を持つ光触媒シートであり、マスクをはじめ、衛生材料、防護服、手袋、ヘアキャップなどのメディカル用途、患者隔離カーテン、インフルエンザパンでミック時の簡易診察用テント、いすカバー、感染者用シーツ、布団カバー、枕カバー、などのほか、空気清浄機、空調用フィルターなどに好適に利用可能である。 The photocatalyst sheet of the present invention has a strong adsorption effect on a virus having an envelope such as influenza virus even in a light-free space or at night, in addition to the virus inactivation effect obtained from the organic substance decomposition effect of UV light of the photocatalyst. It is a photocatalytic sheet with performance, including masks, sanitary materials, protective clothing, gloves, hair caps and other medical uses, patient isolation curtains, flu pans for simple diagnostic tents, chair covers, infected sheets, In addition to futon covers and pillow covers, it can be suitably used for air purifiers, air conditioning filters, and the like.
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| US20220062488A1 (en) * | 2020-08-31 | 2022-03-03 | Promethium Limited | Photoactivated semiconductor photocatalytic air purification |
| US20220062489A1 (en) * | 2020-08-31 | 2022-03-03 | Promethium Limited | Photoactivated semiconductor photocatalytic air purification |
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| JP2014198165A (en) * | 2013-03-29 | 2014-10-23 | アイリスオーヤマ株式会社 | Mask |
| JP6663140B2 (en) * | 2017-12-28 | 2020-03-11 | 合同会社エージェントスタイル | mask |
| KR102471096B1 (en) * | 2020-05-25 | 2022-11-25 | 주식회사 코렌스알티엑스 | Method for fabricating antimicrobial mask using electron beam |
| CN113679124B (en) * | 2021-08-28 | 2023-02-24 | 安徽农业大学 | Recyclable antiviral mask and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10108915A (en) * | 1996-10-03 | 1998-04-28 | Hitachi Chem Co Ltd | Deodorizing mask |
| JPH11315472A (en) * | 1997-11-11 | 1999-11-16 | Nippon Sheet Glass Co Ltd | Nonwoven fabric and its production, and alkali secondary battery using the same |
| TW473400B (en) * | 1998-11-20 | 2002-01-21 | Asahi Chemical Ind | Modified photocatalyst sol |
| JP2000300984A (en) * | 1999-04-22 | 2000-10-31 | Daikin Ind Ltd | Photocatalyst particle-containing polytetrafluoroethylene molding material for paste extrusion molding, its manufacture and molded product using the material |
| JP4739491B2 (en) * | 2000-08-01 | 2011-08-03 | ダイワボウホールディングス株式会社 | Functional fiber sheet and method for producing the same |
| JP2005124777A (en) * | 2003-10-23 | 2005-05-19 | Kurashiki Seni Kako Kk | Infection prevention mask |
| JP2007054381A (en) * | 2005-08-25 | 2007-03-08 | Kurashiki Seni Kako Kk | Cubical mask |
| JP5008359B2 (en) * | 2006-08-23 | 2012-08-22 | 旭化成せんい株式会社 | Non-woven fabric supporting photocatalyst |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20220062488A1 (en) * | 2020-08-31 | 2022-03-03 | Promethium Limited | Photoactivated semiconductor photocatalytic air purification |
| US20220062489A1 (en) * | 2020-08-31 | 2022-03-03 | Promethium Limited | Photoactivated semiconductor photocatalytic air purification |
| US11612673B2 (en) * | 2020-08-31 | 2023-03-28 | Promethium Limited | Photoactivated semiconductor photocatalytic air purification |
| US11623018B2 (en) * | 2020-08-31 | 2023-04-11 | Promethium Limited | Photoactivated semiconductor photocatalytic air purification |
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| JP2011240304A (en) | 2011-12-01 |
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