WO2022196393A1 - Antiviral sheet - Google Patents

Antiviral sheet Download PDF

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Publication number
WO2022196393A1
WO2022196393A1 PCT/JP2022/009412 JP2022009412W WO2022196393A1 WO 2022196393 A1 WO2022196393 A1 WO 2022196393A1 JP 2022009412 W JP2022009412 W JP 2022009412W WO 2022196393 A1 WO2022196393 A1 WO 2022196393A1
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WO
WIPO (PCT)
Prior art keywords
plaster
fiber sheet
antiviral
mask
sheet
Prior art date
Application number
PCT/JP2022/009412
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French (fr)
Japanese (ja)
Inventor
正 藤本
浩喜 平山
Original Assignee
株式会社トクヤマ
正 藤本
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Application filed by 株式会社トクヤマ, 正 藤本 filed Critical 株式会社トクヤマ
Publication of WO2022196393A1 publication Critical patent/WO2022196393A1/en

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    • A—HUMAN NECESSITIES
    • A41—WEARING APPAREL
    • A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
    • A41D13/00—Professional, industrial or sporting protective garments, e.g. surgeons' gowns or garments protecting against blows or punches
    • A41D13/05—Professional, industrial or sporting protective garments, e.g. surgeons' gowns or garments protecting against blows or punches protecting only a particular body part
    • A41D13/11—Protective face masks, e.g. for surgical use, or for use in foul atmospheres
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/44—Oxides or hydroxides of elements of Groups 2 or 12 of the Periodic Table; Zincates; Cadmates
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16—Synthetic fibres, other than mineral fibres
    • D06M2101/18—Synthetic fibres consisting of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M2101/20—Polyalkenes, polymers or copolymers of compounds with alkenyl groups bonded to aromatic groups

Definitions

  • the present invention relates to an antiviral sheet, and more particularly to an antiviral sheet that is made of a fiber sheet and can be suitably used as a mask, protective clothing, and the like.
  • N95 masks are particularly widely known as masks for medical personnel.
  • This N95 mask satisfies the standards established by the National Institute for Occupational Safety and Health (NIOSH), and can collect 95% or more of test particles (for example, NaCl particles) with a size of about 0.3 ⁇ m. can.
  • test particles for example, NaCl particles
  • Patent Document 1 discloses an antiviral agent containing hydroxides of magnesium and calcium obtained by partially hydrating after burning dolomite, and treating a mask with such an antiviral agent. It is described that it imparts antiviral properties by This antiviral property is due to the antioxidant action of hydroxyl radicals.
  • treatment with the above antiviral agent can impart antiviral properties to the mask, but its sustainability has not been studied at all. For example, when using N95 masks continuously or intermittently for 8 hours, even if you cough or sneeze while wearing the mask, more than 99.8% of the virus adhering to the filter inside the mask is trapped in the mask. Up to Therefore, considering that masks are usually used continuously or intermittently for about 8 hours, not only medical masks, but also antiviral effects against viruses adhering to the outer surface of the mask If this is maintained for about 8 hours, contact infection due to contact with the mask will be effectively prevented even if the hands or face come into contact during that time, but such durability has not been studied. The reality is that there is none.
  • an object of the present invention is to provide an antiviral sheet that has excellent long-lasting antiviral properties and effectively prevents contact infection.
  • Another object of the present invention is to provide an antiviral sheet comprising a fiber sheet suitable for masks and protective clothing.
  • an antiviral sheet made of a fiber sheet having plaster carried on its surface is provided.
  • the fiber sheet is a nonwoven fabric.
  • the nonwoven fabric is made of polyolefin.
  • the nonwoven fabric is made of hydrophilic fibers.
  • the total pore volume measured by the nitrogen method is in the range of 0.026 to 0.06 cm 3 /g.
  • the plaster carried on the fiber sheet is subjected to solvent extraction, and the extracted particle size measured by a laser diffraction method is in the range of 2 to 40 ⁇ m.
  • the loading of plaster is in the range of 1.4-4.0 mg/cm 2 . (7) be applied to masks or protective clothing;
  • the antiviral sheet of the present invention has a plaster carried in the vicinity of the surface layer of the fiber sheet, and the plaster exhibits antiviral properties. Plaster is made by absorbing carbon dioxide gas from slaked lime to become calcium carbonate, and contains calcium hydroxide inside. For this reason, it exhibits alkalinity for a long time, and as a result, the antiviral property is continuously exhibited. It is maintained, and along with the filter effect, it is possible to effectively prevent contact infection from the mask surface contaminated with viruses. That is, such an antiviral sheet of the present invention is useful as a mask material for preventing infectious diseases, and is also effectively used as a protective clothing material.
  • FIG. 2 is a diagram for explaining the principle of the present invention.
  • the antiviral sheet of the present invention is a fiber sheet supporting plaster, and the fiber sheet prevents infection by the filter effect and prevents infection by the antiviral property of the plaster (prevention of contact infection). is.
  • non-woven fabric As the fiber sheet, either non-woven fabric or woven fabric can be used. However, from the viewpoint of limiting the size of the openings to ensure the filter effect and breathability to exhibit the performance of breathing or plaster. Non-woven fabrics are preferred.
  • the nonwoven fabric may be obtained by a method known per se using thermoplastic resin fibers, but from a hygienic standpoint, thermal bonded nonwoven fabrics, spunbond nonwoven fabrics, nanofiber nonwoven fabrics obtained without the use of adhesives are preferred. , Spunlace nonwoven fabrics, etc. are used, but thermal bond nonwoven fabrics are preferable in that they can adhere plaster to the surface by plaster treatment and can ensure adequate air permeability.
  • thermoplastic resins forming fibers include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 4-methyl-1-pentene, 5-methyl- Olefin-based resins that are homopolymers or copolymers of ⁇ -olefins such as 1-heptene; polyvinyl chloride, vinyl chloride-vinyl acetate copolymers, vinyl chloride-vinylidene chloride copolymers, vinyl chloride-olefin copolymers Vinyl chloride resins such as coalescence; polytetrafluoroethylene, polychlorotrifluoroethylene, polyvinylidene fluoride, tetrafluoroethylene-hexafluoropropylene copolymer, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, tetrafluoro fluorine-based resins such as ethylene-ethylene copolymer; polyamide resins such as
  • olefin resin fibers are preferred in terms of alkali resistance
  • nonwoven fabrics formed of polypropylene fibers are preferred in consideration of strength and durability.
  • hydrophilic fibers such as cotton are suitable for reducing the burden on the environment upon disposal.
  • the fiber diameter, the basis weight of the fiber, and the like may be set according to the purpose and usage of the fiber sheet so that, for example, the pore volume described later can be secured when treated with plaster.
  • the thickness of the nonwoven fabric sheet may be within an appropriate range depending on the usage pattern.
  • the fiber sheet of the present invention carries plaster.
  • the plaster is a kneaded product (slurry) containing slaked lime (calcium hydroxide) powder and water. can be impregnated and supported by applying it to the surface of the plaster.
  • plaster is in a state of a mixture of slaked lime (calcium hydroxide) and calcium carbonate, and further absorbs carbon dioxide gas in the air. As a result, carbonation progresses from the surface layer of the slaked lime particles to form calcium carbonate.
  • FIG. 1 indicates a mask (fiber sheet), and the outer surface side of the mask 1 is plastered.
  • FIG. 1(A) shows the state of breathing in
  • FIG. 1(B) shows the state of breathing out.
  • the virus adheres to the outer surface of the mask 1. Especially when the user inhales, the virus 3 tends to adhere to the outer surface of the mask 1 along with air currents. Then, when you breathe in, part of the water in the plaster evaporates at the same time as you breathe in, so the CO 2 concentration dissolved in the water rises and carbonation progresses. .
  • the reaction at this time is represented by the following formula as shown in FIG. 1(A). Ca 2+ (aq)+2(OH) ⁇ (aq)+CO 2 (g) ⁇ CaCO 3 (s) + H 2 O (l)
  • the plaster is mostly distributed in the non-fused portion of the fiber sheet, and the virus adheres to the outer surface side of this non-fused portion. It exhibits high antiviral properties at the fused part.
  • the plaster can be supported as described above by impregnating the fiber sheet by dipping or the like using a dispersion (plaster slurry) of slaked lime particles dispersed in water.
  • the solid content concentration of the plaster (total solid content of slaked lime and calcium carbonate) in such a dispersion is generally 5 to 60% by mass, particularly about 8 to 20% by mass.
  • This surface-treated fiber sheet is wrapped with an olefin film or the like to block it from the outside air and prevent carbonation and moisture evaporation. Also, if you need to store it for a longer period of time, you can also pack it in a vacuum pack.
  • the plaster slurry preferably contains a water-soluble organic dispersant such as isopropanol in order to increase affinity with the fiber sheet. This allows the plaster (slaked lime particles) to permeate into the interior of the fiber sheet. Also, in order to prevent the plaster from falling off from the fiber sheet, it is desirable that a polymer emulsion be dispersed as a binder. Examples of such polymer emulsions include aqueous emulsions of polymers such as acrylic resins, polyvinyl acetates, polyurethanes, and styrene/butadiene rubbers. The above-mentioned water-soluble organic dispersant and polymer emulsion are blended into the above-mentioned dispersion within a range in which the slaked lime particles and water are contained at a certain ratio.
  • a water-soluble organic dispersant such as isopropanol
  • the D50 particle size of the slaked lime particles used to prepare the dispersion is preferably in the range of 2 to 40 ⁇ m in order to develop appropriate alkali activity. If the particle size is excessively small, carbonation may proceed rapidly, resulting in insufficient alkali activity. Also, when the particle size is excessively large, the alkali activity tends to decrease.
  • the D50 particle size of the slaked lime particles is published by the manufacturer (manufacturer's nominal value), but the D50 particle size is substantially the same as the solvent extraction particle size of the plaster particles supported on the fiber sheet.
  • the extracted particle size of the plaster particles supported on the fiber sheet is extracted from the fiber sheet using a solvent and measured by a laser diffraction scattering method from the extracted liquid, as described in Examples described later. be able to. This is because a polymer emulsion or the like is contained as a binder in the dispersion for supporting the plaster and must be removed.
  • particles obtained by pulverizing minerals such as dolomite contain calcium hydroxide. shows strong alkaline activity in the initial stage, but the alkaline activity drops rapidly over time, and it has been confirmed that, for example, continuous use for 8 hours does not exhibit sufficient alkaline activity (see Experimental Example 12 described later). This is probably because the pore volume is too large, the dolomite particle size is too small, and the amount of slaked lime supported is not sufficient. That is, from this experimental result, it is clear that Patent Document 1 does not examine the persistence of antiviral properties.
  • the plaster in order for the plaster to exhibit alkali activity, it is necessary that the plaster contains moisture when the mask with the plaster-treated fiber sheet placed on the surface is worn on the human body. It is preferable that the pH of the plaster is maintained at 11 or more even after the passage of time, and in order to maintain this alkaline activity, the average moisture content for 8 hours after wearing the mask is in the range of 8 to 15%. Desirable. Incidentally, the methods for measuring the pH and the average water content are as shown in Examples described later.
  • FIG. 3 shows the relationship between the slaked lime particle diameter D50 (manufacturer's nominal value) used in the preparation of the dispersion liquid and the 8-hour average water content when the water slaked lime ratio is set as a variable, and the ratio is 200 to 250. % moisture content was maximized.
  • FIG. 4 shows the relationship between the water-slaked lime ratio and the alkali activity at each mask wearing time, and the alkali activity after 8 hours has the same tendency as the 8-hour average water content. A significant correlation was observed.
  • FIG. 9 plots Experimental Examples 1 to 8.
  • the extracted particle diameter D50 which is obtained by solvent-extracting the plaster from the plaster-treated fiber sheet and measuring it by a laser diffraction method, is in the range of 2 to 40 ⁇ m, particularly 3 to 20 ⁇ m. Within this average particle size range, the average moisture content for 8 hours after wearing the mask is high, and excellent antiviral properties can be maintained.
  • FIG. 5 is a relationship curve with the 8-hour average water content when the water slaked lime ratio is fixed at 220% and the D50 particle size (manufacturer's nominal value) of the used slaked lime is used as a variable. At times the water content is maximum.
  • FIG. 6 is a relationship curve between the D50 particle size and the alkali activity for each mask wearing time, and the alkali activity after 8 hours has the same tendency as the 8-hour average moisture content. As shown in FIG. 9, which shows the relationship curve between the 8-hour average moisture content and alkali activity, a linear correlation is recognized between the two.
  • the plaster-treated fiber sheet has a total pore volume (pore volume with a pore diameter of 1 to 300 nm) measured by the nitrogen method in order to maintain antiviral properties due to alkali activity for about 8 hours. It is desirable to be in the range of 0.026-0.06 cm 3 /g, particularly 0.03-0.05 cm 3 /g. Within this range of pore volume, the average water content for 8 hours after wearing the mask is high, and excellent antiviral properties can be maintained.
  • the horizontal axis is the total pore volume
  • the vertical axis is the 8-hour average water content (FIG. 7) and the alkali activity (FIG. 8).
  • the test results with different variables of the water slaked lime ratio (Experimental Examples 1 to 4) and the D50 particle size (Experimental Examples 5 to 8) can be on the same calibration curve. found. Therefore, the total pore volume is considered an important parameter for evaluating the sustainability of alkaline activity.
  • the amount of plaster supported (total amount of solid content of calcium hydroxide and calcium carbonate) is in the range of 1.4 to 4.0 mg/cm 2 , particularly 2.0 to 3.5 mg/cm 2 . desirable. If the amount is too large, the breathability of the plaster-treated fiber sheet may be impaired, and if it is too small, the alkali activity that exerts the antiviral properties will naturally decrease.
  • Such plaster-treated fiber sheets are suitably used for applications such as masks and protective clothing to prevent viral infection, and various physical properties are adjusted so that antiviral properties can be exhibited for at least about 8 hours.
  • a plurality of sheets can be stacked and used.
  • a flexible sheet (plastered fiber sheet) is used.
  • the surface support by plaster may be carried out at least on the outer surface side of the fiber sheet, and the plaster treatment on the inner surface side may be omitted.
  • Extraction particle size of the stucco carried on the fiber sheet A plaster-treated fiber sheet having a size of 100 mm ⁇ 100 mm was cut into a size of 5 mm ⁇ 5 mm, stirred in toluene with a stirrer for 3 hours, and then the fiber sheet was taken out. The remaining toluene solution was allowed to stand to separate the sedimented plaster, which was repeatedly washed with toluene to remove the acrylic content, and then dried to extract powdery plaster.
  • the particle size distribution was measured using a laser diffraction method with a water solvent in accordance with JIS Z 8825, and the mode diameter obtained was It was taken as the extracted particle size ( ⁇ m).
  • the moisture content (M n ) for each n hours of wearing the mask was calculated from the following formula using the mass (W n ) measured for each hour.
  • Water content (%) [(W n - W 01 )/W 01 + (W 02 - W D2 )/W D2 ]/100
  • the alkaline activity determination test by adding water for 4 seconds aims at reproducing the alkaline activity by intermittent water supply from the exhaled breath occurring in each respiratory cycle, in line with the principle described above.
  • Example 9 A plaster-carrying fiber sheet was obtained by impregnating and applying a mixed solution containing slaked lime prepared by changing the plaster-carrying amount in Experimental Example 3 to the values shown in Table 3 by a dipping method. Further, a performance evaluation mask was obtained in the same manner as in Experimental Example 1. Table 4 shows the obtained water content and alkaline activity test results.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Physical Education & Sports Medicine (AREA)
  • Laminated Bodies (AREA)
  • Medicinal Preparation (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
  • Respiratory Apparatuses And Protective Means (AREA)
  • Nonwoven Fabrics (AREA)

Abstract

An antiviral sheet that comprises a fiber sheet holding plaster.

Description

抗ウイルス性シートantiviral sheet
　本発明は、抗ウイルス性シートに関するものであり、より詳細には、繊維シートからなり、マスクや防護服などとして好適に使用し得る抗ウイルス性シートに関する。 The present invention relates to an antiviral sheet, and more particularly to an antiviral sheet that is made of a fiber sheet and can be suitably used as a mask, protective clothing, and the like.
　近年、ＳＡＲＳ、新型コロナ感染症、インフルエンザなどの呼吸器感染症の予防のためにマスクの着用が求められており、特に医療関係者用のマスクとして、Ｎ９５マスクが広く知られている。このＮ９５マスクは、米国立労働安全衛生研究所（ＮＩＯＳＨ）が定めた規格を満足するものであり、約０．３μｍの大きさの試験粒子（例えばＮａＣｌ粒子）を９５％以上捕集することができる。Ｎ９５マスクに代表される公知のマスクは、フィルターとしての機能を有するものではあるが、抗ウイルス性は有していない。 In recent years, there has been a demand for wearing masks to prevent respiratory infections such as SARS, new coronavirus infections, and influenza, and N95 masks are particularly widely known as masks for medical personnel. This N95 mask satisfies the standards established by the National Institute for Occupational Safety and Health (NIOSH), and can collect 95% or more of test particles (for example, NaCl particles) with a size of about 0.3 μm. can. Known masks, typified by N95 masks, function as filters but do not have antiviral properties.
　一方、特許文献１には、ドロマイトを焼成した後、部分水和することで得られるマグネシウム及びカルシウムの水酸化物を含む抗ウイルス剤が開示されており、このような抗ウイルス剤によりマスクを処理して抗ウイルス性を付与することが記載されている。この抗ウイルス性は、ヒドロキシラジカルによる抗酸化作用によるものである。 On the other hand, Patent Document 1 discloses an antiviral agent containing hydroxides of magnesium and calcium obtained by partially hydrating after burning dolomite, and treating a mask with such an antiviral agent. It is described that it imparts antiviral properties by This antiviral property is due to the antioxidant action of hydroxyl radicals.
　即ち、上記の抗ウイルス剤で処理することにより、マスクに抗ウイルス性を付与することができるのであるが、その持続性については全く検討されていない。例えば、Ｎ９５マスクは、８時間の連続或いは断続使用に対して、マスク装着状態で咳やくしゃみなどをしてもマスク内部のフィルターに付着したウイルスのほぼ９９．８％以上はマスクに閉じ込められたままである。従って、マスクは、通常、８時間程度の継続的或いは断続的使用に供されるものであることを考えれば、医療用マスクに限らず、マスク外側の表面に付着したウイルスに対し、抗ウイルス効果が約８時間程度維持されれば、その間に手や顔などが接触したとしても、マスク接触による接触感染は有効に防止されることになるのであるが、このような持続性については検討されていないのが実情である。 In other words, treatment with the above antiviral agent can impart antiviral properties to the mask, but its sustainability has not been studied at all. For example, when using N95 masks continuously or intermittently for 8 hours, even if you cough or sneeze while wearing the mask, more than 99.8% of the virus adhering to the filter inside the mask is trapped in the mask. Up to Therefore, considering that masks are usually used continuously or intermittently for about 8 hours, not only medical masks, but also antiviral effects against viruses adhering to the outer surface of the mask If this is maintained for about 8 hours, contact infection due to contact with the mask will be effectively prevented even if the hands or face come into contact during that time, but such durability has not been studied. The reality is that there is none.
特許第４６２１５９０号公報Japanese Patent No. 4621590
　従って、本発明の目的は、抗ウイルス性の持続性に優れ、接触感染が有効に防止された抗ウイルス性シートを提供することにある。
　本発明の他の目的は、マスクや防護服に好適に適用される繊維シートからなる抗ウイルス性シートを提供することにある。 SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide an antiviral sheet that has excellent long-lasting antiviral properties and effectively prevents contact infection.
Another object of the present invention is to provide an antiviral sheet comprising a fiber sheet suitable for masks and protective clothing.
　本発明によれば、漆喰が表面に担持されている繊維シートからなる抗ウイルス性シートが提供される。 According to the present invention, an antiviral sheet made of a fiber sheet having plaster carried on its surface is provided.
　本発明の抗ウイルス性シートにおいては、次の態様が好適に採用される。
（１）前記繊維シートが不織布であること。
（２）前記不織布がポリオレフィン製であること。
（３）前記不織布が親水性繊維からなること。
（４）窒素法で測定した全細孔容積が０．０２６～０．０６ｃｍ３／ｇの範囲にあること。
（５）前記繊維シートに担持されている漆喰を溶剤抽出し、レーザー回折法で測定した抽出粒子径が２～４０μｍの範囲にあること。
（６）漆喰の担持量が１．４～４．０ｍｇ／ｃｍ２の範囲にあること。
（７）マスク或いは防護服に適用されること。 The following aspects are preferably employed in the antiviral sheet of the present invention.
(1) The fiber sheet is a nonwoven fabric.
(2) The nonwoven fabric is made of polyolefin.
(3) The nonwoven fabric is made of hydrophilic fibers.
(4) The total pore volume measured by the nitrogen method is in the range of 0.026 to 0.06 cm 3 /g.
(5) The plaster carried on the fiber sheet is subjected to solvent extraction, and the extracted particle size measured by a laser diffraction method is in the range of 2 to 40 μm.
(6) The loading of plaster is in the range of 1.4-4.0 mg/cm 2 .
(7) be applied to masks or protective clothing;
　本発明の抗ウイルス性シートは、繊維シートの表層付近に漆喰が担持されているものであり、この漆喰により抗ウイルス性を発現させたものである。漆喰は消石灰が炭酸ガスを吸収して炭酸カルシウムとなったものであり、水酸化カルシウムを内部に含んでいる。このため、長時間にわたってアルカリ性を呈し、これにより、抗ウイルス性が持続して発揮され、例えばマスク等に適用した場合、Ｎ９５マスクなどに要求される８時間程度の連続使用中、抗ウイルス性が維持されており、フィルター効果とともに、ウイルスで汚染されたマスク表面からの接触感染を有効に防止することができる。
　即ち、このような本発明の抗ウイルス性シートは、感染症予防のためのマスク素材として有用であり、防護服素材としても有効に使用される。 The antiviral sheet of the present invention has a plaster carried in the vicinity of the surface layer of the fiber sheet, and the plaster exhibits antiviral properties. Plaster is made by absorbing carbon dioxide gas from slaked lime to become calcium carbonate, and contains calcium hydroxide inside. For this reason, it exhibits alkalinity for a long time, and as a result, the antiviral property is continuously exhibited. It is maintained, and along with the filter effect, it is possible to effectively prevent contact infection from the mask surface contaminated with viruses.
That is, such an antiviral sheet of the present invention is useful as a mask material for preventing infectious diseases, and is also effectively used as a protective clothing material.
本発明の原理を説明するための図。FIG. 2 is a diagram for explaining the principle of the present invention; 漆喰処理繊維シートが使用されているマスクにおいて、マスク装着時間と含水率との関係を示す図。The figure which shows the relationship between mask wearing time and moisture content in the mask in which the plaster treatment fiber sheet is used. 漆喰処理繊維シートの水消石灰比と８時間平均含水率との関係を示す図。The figure which shows the relationship between the water-slaked-lime ratio of a mortar processing fiber sheet, and an 8-hour average moisture content. 漆喰処理繊維シートの水消石灰比とアルカリ活性との関係を示す図。The figure which shows the relationship between the water-slaked-lime ratio of a mortar processing fiber sheet, and alkali activity. 漆喰処理繊維シートへの担持に用いた消石灰の粒子径と８時間平均含水率との関係を示す図。The figure which shows the relationship between the particle diameter of the hydrated lime used for carrying|support to a stucco processing fiber sheet, and an 8-hour average moisture content. 漆喰処理繊維シートへの担持に用いた消石灰の粒子径とアルカリ活性との関係を示す図。The figure which shows the relationship between the particle size of the hydrated lime used for carrying|support to a stucco processing fiber sheet, and alkali activity. 漆喰処理繊維シートの全細孔容積と８時間平均含水率との関係を示す図。The figure which shows the relationship between the total pore volume of a stucco processing fiber sheet, and an 8-hour average moisture content. 漆喰処理繊維シートの全細孔容積とアルカリ活性との関係を示す図。The figure which shows the relationship between the total pore volume of a stucco processing fiber sheet, and alkali activity. 漆喰処理繊維シートの８時間平均含水率とアルカリ活性との関係を示す図。The figure which shows the relationship between the 8-hour average moisture content of a plaster treatment fiber sheet, and alkali activity.
　本発明の抗ウイルス性シートは、繊維シートに漆喰を担持させたものであり、繊維シートによりフィルター効果による感染防止と、漆喰による抗ウイルス性による感染防止（接触感染防止）とを発現させたものである。 The antiviral sheet of the present invention is a fiber sheet supporting plaster, and the fiber sheet prevents infection by the filter effect and prevents infection by the antiviral property of the plaster (prevention of contact infection). is.
　繊維シートとしては、不織布、織布の何れも使用することができるが、フィルター効果を確保するための開口の大きさを制限し、且つ呼吸或いは漆喰の性能発揮のための通気性などの観点から不織布が好適である。 As the fiber sheet, either non-woven fabric or woven fabric can be used. However, from the viewpoint of limiting the size of the openings to ensure the filter effect and breathability to exhibit the performance of breathing or plaster. Non-woven fabrics are preferred.
　不織布は、熱可塑性樹脂製の繊維を用いてそれ自体公知の方法で得られるものでよいが、衛生的見地から、接着剤を使用せずに得られるサーマルボンド不織布、スパンボンド不織布、ナノファイバー不織布、スパンレース不織布などを使用されるが、漆喰処理により表面に漆喰を付着させることができ、且つ適度な通気性を確保することができるという点でサーマルボンド不織布が好適である。 The nonwoven fabric may be obtained by a method known per se using thermoplastic resin fibers, but from a hygienic standpoint, thermal bonded nonwoven fabrics, spunbond nonwoven fabrics, nanofiber nonwoven fabrics obtained without the use of adhesives are preferred. , Spunlace nonwoven fabrics, etc. are used, but thermal bond nonwoven fabrics are preferable in that they can adhere plaster to the surface by plaster treatment and can ensure adequate air permeability.
　また、繊維を形成する熱可塑性樹脂の例としては、エチレン、プロピレン、１－ブテン、１－ペンテン、１－ヘキセン、３－メチル－１－ブテン、４－メチル－１－ペンテン、５－メチル－１－ヘプテン等のα－オレフィンの単独重合体また共重合体であるオレフィン系樹脂；ポリ塩化ビニル、塩化ビニル－酢酸ビニル共重合体、塩化ビニル－塩化ビニリデン共重合体、塩化ビニル－オレフィン共重合体等の塩化ビニル系樹脂；ポリテトラフルオロエチレン、ポリクロロトリフルオロエチレン、ポリフッ化ビニリデン、テトラフルオロエチレン－ヘキサフルオロプロピレン共重合体、テトラフロオロエチレン－ペルフロオロアルキルビニルエーテル共重合体、テトラフルオロエチレン－エチレン共重合体等のフッ素系樹脂；ナイロン６、ナイロン６６等のポリアミド樹脂；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、ポリトリメチレンテレフタレートなどのポリエステル系樹脂等を挙げることができる。
　これらの中でも、耐アルカリ性という点でオレフィン系樹脂繊維（特に、ポリエチレン繊維、ポリプロピレン繊維）が好ましく、強度や耐久性を考慮すると、ポリプロピレン製繊維で形成された不織布が好適である。
　また、コットンなどの親水性繊維は、廃棄に際しての環境に与える負荷軽減の上で好適である。 Examples of thermoplastic resins forming fibers include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 4-methyl-1-pentene, 5-methyl- Olefin-based resins that are homopolymers or copolymers of α-olefins such as 1-heptene; polyvinyl chloride, vinyl chloride-vinyl acetate copolymers, vinyl chloride-vinylidene chloride copolymers, vinyl chloride-olefin copolymers Vinyl chloride resins such as coalescence; polytetrafluoroethylene, polychlorotrifluoroethylene, polyvinylidene fluoride, tetrafluoroethylene-hexafluoropropylene copolymer, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, tetrafluoro fluorine-based resins such as ethylene-ethylene copolymer; polyamide resins such as nylon 6 and nylon 66; polyester-based resins such as polyethylene terephthalate, polybutylene terephthalate and polytrimethylene terephthalate.
Among these, olefin resin fibers (particularly polyethylene fibers and polypropylene fibers) are preferred in terms of alkali resistance, and nonwoven fabrics formed of polypropylene fibers are preferred in consideration of strength and durability.
Also, hydrophilic fibers such as cotton are suitable for reducing the burden on the environment upon disposal.
　また、繊維径、繊維の目付量などは、この繊維シートの用途や使用形態などに応じて、例えば、漆喰で処理したときに後述する細孔容積を確保できるように設定されればよく、同様に、不織布シートの厚みも、その使用形態に応じて適宜の範囲にあればよい。 In addition, the fiber diameter, the basis weight of the fiber, and the like may be set according to the purpose and usage of the fiber sheet so that, for example, the pore volume described later can be secured when treated with plaster. In addition, the thickness of the nonwoven fabric sheet may be within an appropriate range depending on the usage pattern.
　本発明の繊維シートは、漆喰が担持されたものであるが、この漆喰は、消石灰（水酸化カルシウム）の粉末と水を含む混練物（スラリー）であり、このようなスラリーをシートの少なくとも一方の表面に塗布することにより、含侵担持することができる。 The fiber sheet of the present invention carries plaster. The plaster is a kneaded product (slurry) containing slaked lime (calcium hydroxide) powder and water. can be impregnated and supported by applying it to the surface of the
　即ち、漆喰は、消石灰が空気中の炭酸ガスを吸収して炭酸カルシウムを形成するため、消石灰（水酸化カルシウム）と炭酸カルシウムとの混合物の状態にあり、さらに空気中の炭酸ガスを吸収することにより、消石灰粒子の表層から炭酸化が進行して炭酸カルシウムが生成していくというものである。 That is, since slaked lime absorbs carbon dioxide gas in the air to form calcium carbonate, plaster is in a state of a mixture of slaked lime (calcium hydroxide) and calcium carbonate, and further absorbs carbon dioxide gas in the air. As a result, carbonation progresses from the surface layer of the slaked lime particles to form calcium carbonate.
　このような漆喰が繊維シートの表層付近に多く付着していることにより抗ウイルス性が持続して発揮されるのであるが、この原理を、マスクを例にとって説明する。
　図１において、１はマスク（繊維シート）を示すものであり、マスク１の外面側が漆喰処理されている。図１（Ａ）は、息を吸うときの状態を示し、図１（Ｂ）は、息を吐くときの状態を示したものである。 Since such plaster adheres to the vicinity of the surface layer of the fiber sheet in a large amount, the antiviral property is continuously exhibited, and this principle will be explained using a mask as an example.
In FIG. 1, 1 indicates a mask (fiber sheet), and the outer surface side of the mask 1 is plastered. FIG. 1(A) shows the state of breathing in, and FIG. 1(B) shows the state of breathing out.
　図１（Ａ）に示されているように、マスク１の外面にウイルスが付着するが、特に息を吸った時、気流に乗ってウイルス３がマスク１の外面に付着しやすい。そして息を吸った時に、漆喰中に存在する水分の一部が息を吸うタイミングで蒸発するため、水分に溶解している呼気由来のＣＯ２濃度が上昇して炭酸化が進行することとなる。
　このときの反応は、図１（Ａ）に示されているように、下記式で表される。
　　Ｃａ２＋（ａｑ）＋２（ＯＨ）－（ａｑ）＋ＣＯ２（ｇ）
　　　　→　ＣａＣＯ３（ｓ）＋Ｈ２Ｏ（ｌ） As shown in FIG. 1(A), the virus adheres to the outer surface of the mask 1. Especially when the user inhales, the virus 3 tends to adhere to the outer surface of the mask 1 along with air currents. Then, when you breathe in, part of the water in the plaster evaporates at the same time as you breathe in, so the CO 2 concentration dissolved in the water rises and carbonation progresses. .
The reaction at this time is represented by the following formula as shown in FIG. 1(A).
Ca 2+ (aq)+2(OH) − (aq)+CO 2 (g)
→ CaCO 3 (s) + H 2 O (l)
　そして、息を吐いたときは、図１（Ｂ）に示されているように、呼気中のＣＯ２と共に、水分がマスク１の内面から外面側に透過する。この水分が漆喰に付着することでアルカリ活性が増すため、マスク１の外面側、即ち、人の手等が接触する側に存在するウイルスを攻撃し、ウイルスを死滅させることとなる。尚、このようなマスク１の外面側の漆喰によるアルカリ活性は、フェノールフタレイン溶液の呈色反応により確認することができる。 Then, when exhaling, as shown in FIG. 1(B), water permeates from the inner surface of the mask 1 to the outer surface side together with CO 2 in the exhaled breath. Since this moisture adheres to the plaster and increases the alkaline activity, it attacks and kills the virus existing on the outer surface side of the mask 1, that is, the side that comes into contact with human hands. The alkali activity of the plaster on the outer surface of the mask 1 can be confirmed by the color reaction of the phenolphthalein solution.
　上記の原理から理解されるように、サーマルボンド不織布の場合、漆喰は、繊維シートにおける繊維の非融着部に多く分布し、この非融着部の外面側にウイルスが付着するため、この非融着部に於いて高い抗ウイルス性を示す。 As can be understood from the above principle, in the case of the thermal bond nonwoven fabric, the plaster is mostly distributed in the non-fused portion of the fiber sheet, and the virus adheres to the outer surface side of this non-fused portion. It exhibits high antiviral properties at the fused part.
　本発明において、上記のような漆喰の担持は、消石灰粒子を水に分散させた分散液（漆喰スラリー）を使用し、ディッピング等により繊維シートを含侵することにより行うことができる。かかる分散液での漆喰の固形分濃度（消石灰と炭酸カルシウムとの合計の固形分）は、一般に、５～６０質量％、特に８～２０質量％程度でよく、塗布後は、使用時まで、この表面処理繊維シートをオレフィンフィルム等により包装し、外気と遮断して炭酸化や水分の蒸発が防止される。また、さらに長期間の保存を要する場合には、真空パックで包装する対応もある。 In the present invention, the plaster can be supported as described above by impregnating the fiber sheet by dipping or the like using a dispersion (plaster slurry) of slaked lime particles dispersed in water. The solid content concentration of the plaster (total solid content of slaked lime and calcium carbonate) in such a dispersion is generally 5 to 60% by mass, particularly about 8 to 20% by mass. This surface-treated fiber sheet is wrapped with an olefin film or the like to block it from the outside air and prevent carbonation and moisture evaporation. Also, if you need to store it for a longer period of time, you can also pack it in a vacuum pack.
　尚、この漆喰スラリーには、繊維シートとの親和性を高めるために、イソプロパノール等の水溶性有機分散剤が配合されていることが好ましい。これにより、繊維シートの内部にまで漆喰（消石灰粒子）を浸透させることができる。また、漆喰の繊維シートからの脱落を防止するために、バインダーとしてポリマーエマルジョンが分散されていることが望ましい。このようなポリマーエマルジョンとしては、アクリル樹脂、ポリ酢酸ビニル、ポリウレタン、スチレン／ブタジエンゴム等の重合体の水性エマルジョンを挙げることができる。
　上述した水溶性有機分散剤やポリマーエマルジョンは、消石灰粒子及び水が一定割合で含まれる範囲内で上記分散液に配合される。 The plaster slurry preferably contains a water-soluble organic dispersant such as isopropanol in order to increase affinity with the fiber sheet. This allows the plaster (slaked lime particles) to permeate into the interior of the fiber sheet. Also, in order to prevent the plaster from falling off from the fiber sheet, it is desirable that a polymer emulsion be dispersed as a binder. Examples of such polymer emulsions include aqueous emulsions of polymers such as acrylic resins, polyvinyl acetates, polyurethanes, and styrene/butadiene rubbers.
The above-mentioned water-soluble organic dispersant and polymer emulsion are blended into the above-mentioned dispersion within a range in which the slaked lime particles and water are contained at a certain ratio.
　また、上記分散液の調製に用いる消石灰粒子のＤ５０粒子径は、２～４０μｍの範囲にあることが適度なアルカリ活性を発現させる上で好適である。この粒径が過度に小さいと、炭酸化が急激に進行してしまい、アルカリ活性が不十分となるおそれがある。また、過度に粒径が大きい場合にもアルカリ活性が低下する傾向がある。なお、この消石灰粒子のＤ５０粒子径は、メーカーにより公表されているが（メーカー公称値）、このＤ５０粒子径は、繊維シートに担持されている漆喰粒子の溶媒抽出粒子径と実質的に同程度であることを確認している。即ち、繊維シートに担持されている漆喰粒子の抽出粒子径は、後述する実施例に記載されているように、溶媒を用いて繊維シートから抽出し、この抽出液からレーザー回折散乱法により測定することができる。漆喰を担持させるための分散液中には、バインダーとしてポリマーエマルジョン等が含まれているため、これを除去する必要があるからである。 In addition, the D50 particle size of the slaked lime particles used to prepare the dispersion is preferably in the range of 2 to 40 μm in order to develop appropriate alkali activity. If the particle size is excessively small, carbonation may proceed rapidly, resulting in insufficient alkali activity. Also, when the particle size is excessively large, the alkali activity tends to decrease. The D50 particle size of the slaked lime particles is published by the manufacturer (manufacturer's nominal value), but the D50 particle size is substantially the same as the solvent extraction particle size of the plaster particles supported on the fiber sheet. It is confirmed that That is, the extracted particle size of the plaster particles supported on the fiber sheet is extracted from the fiber sheet using a solvent and measured by a laser diffraction scattering method from the extracted liquid, as described in Examples described later. be able to. This is because a polymer emulsion or the like is contained as a binder in the dispersion for supporting the plaster and must be removed.
　さらに、ドロマイトのような鉱物を粉砕して得られる粒子には、水酸化カルシウムが含まれているが、特許文献１に記載されているようなドロマイト粒子（抗ウイルス剤）を担持させた繊維シートは、初期は強いアルカリ活性を示すが、経時と共に急激にアルカリ活性が低下し、例えば８時間継続使用では、十分なアルカリ活性を示さないことが確認されている（後述する実験例１２参照）。これは、おそらく、細孔容積が大き過ぎる、ドロマイト粒子径が小さ過ぎ、消石灰としての担持量も十分とはならないことなどが原因と考えられる。即ち、この実験結果からも、特許文献１では、抗ウイルス性の持続性は検討されてないことが明らかである。 Furthermore, particles obtained by pulverizing minerals such as dolomite contain calcium hydroxide. shows strong alkaline activity in the initial stage, but the alkaline activity drops rapidly over time, and it has been confirmed that, for example, continuous use for 8 hours does not exhibit sufficient alkaline activity (see Experimental Example 12 described later). This is probably because the pore volume is too large, the dolomite particle size is too small, and the amount of slaked lime supported is not sufficient. That is, from this experimental result, it is clear that Patent Document 1 does not examine the persistence of antiviral properties.
　さらに付け加えると、漆喰がアルカリ活性を示すためには、この漆喰処理繊維シートを表面に設置したマスクを人体に装着した状態で漆喰が水分を含有していることが必要であり、マスク装着後８時間経過後でも、漆喰のｐＨが１１以上に維持されていることが好ましく、このアルカリ活性を維持させるために、マスク装着後８時間平均含水率が８～１５％の範囲にあることが望ましい。尚、これらｐＨや平均含水率の測定法は、後述する実施例に示すとおりである。 In addition, in order for the plaster to exhibit alkali activity, it is necessary that the plaster contains moisture when the mask with the plaster-treated fiber sheet placed on the surface is worn on the human body. It is preferable that the pH of the plaster is maintained at 11 or more even after the passage of time, and in order to maintain this alkaline activity, the average moisture content for 8 hours after wearing the mask is in the range of 8 to 15%. Desirable. Incidentally, the methods for measuring the pH and the average water content are as shown in Examples described later.
　例えば、この漆喰処理繊維シートを表装に設置したマスクを人体に装着すると、後述する実験例の結果をまとめた図２に示すように、装着後１～２時間は吐く息による加水量が吸う息による乾燥を上回って含水率が増加し、その後装着８時間まで同含水率は維持される。８時間平均含水率が８～１５％の場合、漆喰粒子の表面が保持された水分によって十分覆われることとなり、前記原理で述べた息を吸うタイミングでの水分乾燥による炭酸化の進行を抑制し、アルカリ活性が維持できると考えられる。 For example, when a mask with this plaster-treated fiber sheet mounted on the surface is worn on the human body, as shown in FIG. The moisture content increases beyond drying by drying, and the same moisture content is maintained until 8 hours after wearing. When the 8-hour average moisture content is 8 to 15%, the surface of the plaster particles is sufficiently covered with the retained moisture, and the progress of carbonation due to moisture drying at the timing of breathing described in the principle above is suppressed. , the alkaline activity can be maintained.
　図３は、分散液の調製に用いた消石灰粒子径Ｄ５０（メーカー公称値）を８μｍで固定し、水消石灰比を変数とした時の８時間平均含水率との関係で、同比が２００～２５０％の時に含水率が最大化された。一方、図４は水消石灰比とマスク装着時間毎でのアルカリ活性との関係で、８時間後のアルカリ活性は８時間平均含水率と同じ傾向であり、図９に示す通り、両者にはリニアな相関が認められた。尚、図９は実験例１～８をプロットした。 FIG. 3 shows the relationship between the slaked lime particle diameter D50 (manufacturer's nominal value) used in the preparation of the dispersion liquid and the 8-hour average water content when the water slaked lime ratio is set as a variable, and the ratio is 200 to 250. % moisture content was maximized. On the other hand, FIG. 4 shows the relationship between the water-slaked lime ratio and the alkali activity at each mask wearing time, and the alkali activity after 8 hours has the same tendency as the 8-hour average water content. A significant correlation was observed. Incidentally, FIG. 9 plots Experimental Examples 1 to 8.
　また、漆喰処理繊維シートから漆喰を溶剤抽出し、レーザー回折法で測定した抽出粒子径Ｄ５０は、２～４０μｍ、特に３～２０μｍの範囲にあることが望ましい。この平均粒子径の範囲であればマスク装着８時間平均含水率が高く、優れた抗ウイルス性が維持できる。 In addition, it is desirable that the extracted particle diameter D50, which is obtained by solvent-extracting the plaster from the plaster-treated fiber sheet and measuring it by a laser diffraction method, is in the range of 2 to 40 μm, particularly 3 to 20 μm. Within this average particle size range, the average moisture content for 8 hours after wearing the mask is high, and excellent antiviral properties can be maintained.
　図５は水消石灰比を２２０％で固定し、用いた消石灰のＤ５０粒子径（メーカー公称値）を変数とした時の８時間平均含水率との関係曲線であり、粒子径が２～４０μｍの時に含水率は最大となっている。
　一方、図６はＤ５０粒子径とマスク装着時間毎でのアルカリ活性との関係曲線であり、８時間後のアルカリ活性は同８時間平均含水率と同じ傾向である。
　８時間平均含水率とアルカリ活性との関係曲線を示す図９に示されているように、両者の間にリニアな相関が認められている。 FIG. 5 is a relationship curve with the 8-hour average water content when the water slaked lime ratio is fixed at 220% and the D50 particle size (manufacturer's nominal value) of the used slaked lime is used as a variable. At times the water content is maximum.
On the other hand, FIG. 6 is a relationship curve between the D50 particle size and the alkali activity for each mask wearing time, and the alkali activity after 8 hours has the same tendency as the 8-hour average moisture content.
As shown in FIG. 9, which shows the relationship curve between the 8-hour average moisture content and alkali activity, a linear correlation is recognized between the two.
　本発明において、漆喰処理繊維シートは、特にアルカリ活性による抗ウイルス性を８時間程度維持させるために、窒素法で測定した全細孔容積（細孔直径が１～３００ｎｍでの細孔容積）が０．０２６～０．０６ｃｍ３／ｇ、特に０．０３～０．０５ｃｍ３／ｇの範囲にあることが望ましい。この細孔容積の範囲内であればマスク装着８時間平均含水率が高く、優れた抗ウイルス性が維持できる。 In the present invention, the plaster-treated fiber sheet has a total pore volume (pore volume with a pore diameter of 1 to 300 nm) measured by the nitrogen method in order to maintain antiviral properties due to alkali activity for about 8 hours. It is desirable to be in the range of 0.026-0.06 cm 3 /g, particularly 0.03-0.05 cm 3 /g. Within this range of pore volume, the average water content for 8 hours after wearing the mask is high, and excellent antiviral properties can be maintained.
　例えば、図７及び図８には、後述する実験例の結果から、全細孔容積を横軸とし、８時間平均含水率（図７）及びアルカリ活性（図８）を縦軸に取った曲線が示されており、図７、図８共に、水消石灰比（実験例１～４）及びＤ５０粒子径（実験例５～８）の夫々異なる変数による試験結果が同一の検量線に載ることが判明した。従って、全細孔容積は、アルカリ活性の持続性を評価する上で重要なパラメータと考えられる。 For example, in FIGS. 7 and 8, the horizontal axis is the total pore volume, and the vertical axis is the 8-hour average water content (FIG. 7) and the alkali activity (FIG. 8). is shown, and in both FIGS. 7 and 8, the test results with different variables of the water slaked lime ratio (Experimental Examples 1 to 4) and the D50 particle size (Experimental Examples 5 to 8) can be on the same calibration curve. found. Therefore, the total pore volume is considered an important parameter for evaluating the sustainability of alkaline activity.
　さらに、漆喰の担持量（水酸化カルシウムと炭酸カルシウムとの固形分合計量）は、１．４～４．０ｍｇ／ｃｍ２、特に２．０～３．５ｍｇ／ｃｍ２の範囲にあることが望ましい。この量が多すぎると、漆喰処理繊維シートの通気性を阻害するおそれがあり、少ないと、当然のことながら、抗ウイルス性を発揮させるアルカリ活性が低くなってしまう。 Furthermore, the amount of plaster supported (total amount of solid content of calcium hydroxide and calcium carbonate) is in the range of 1.4 to 4.0 mg/cm 2 , particularly 2.0 to 3.5 mg/cm 2 . desirable. If the amount is too large, the breathability of the plaster-treated fiber sheet may be impaired, and if it is too small, the alkali activity that exerts the antiviral properties will naturally decrease.
　このような漆喰処理繊維シートは、ウイルス感染防止のため、マスクや防護服などの用途に好適に使用され、少なくとも８時間程度は抗ウイルス性を発揮できるように、各種物性が調整される。
　また、フィルター効果を高めるために複数枚を重ねて使用することができるが、複数枚を重ねて使用する形態（例えば医療用マスク）では、外面側に存在する繊維シートとして、本発明の抗ウイルス性シート（漆喰処理繊維シート）が使用される。
　さらに、漆喰よる表面担持は、少なくとも繊維シートの外面側が処理されていればよく、内面側の漆喰処理を省略することもできる。 Such plaster-treated fiber sheets are suitably used for applications such as masks and protective clothing to prevent viral infection, and various physical properties are adjusted so that antiviral properties can be exhibited for at least about 8 hours.
In addition, in order to enhance the filter effect, a plurality of sheets can be stacked and used. A flexible sheet (plastered fiber sheet) is used.
Furthermore, the surface support by plaster may be carried out at least on the outer surface side of the fiber sheet, and the plaster treatment on the inner surface side may be omitted.
　本発明を、次の実験例で説明する。
　なお、以下の実験で用いた各試験評価方法および材料を示す。 The invention is illustrated by the following experimental examples.
In addition, each test evaluation method and material used in the following experiments are shown.
漆喰の担持量；
　１００ｍｍ×１００ｍｍサイズの漆喰処理繊維シートを１００℃、５分間乾燥させた質量（Ｗｆｓ）を測定した後、５ｍｍ×５ｍｍのサイズに刻んで、１Ｎ塩酸中でスターラーにて３時間攪拌した後、水で洗浄し漆喰成分を全て分離した。その後、繊維シートの水分を１００℃、５分間乾燥させて乾燥質量（Ｗｆ）を得た。下記式により、漆喰の担持量（Ｗｓ）を求めた。
　　漆喰担持量Ｗｓ（ｍｇ／ｃｍ２）＝（Ｗｆｓ－Ｗｆ）／１００ loading of stucco;
A 100 mm × 100 mm size plaster-treated fiber sheet was dried at 100 ° C. for 5 minutes, and the mass (Wfs) was measured, then cut into 5 mm × 5 mm sizes, stirred in 1N hydrochloric acid with a stirrer for 3 hours, and then water. to separate all plaster components. Thereafter, the moisture content of the fiber sheet was dried at 100° C. for 5 minutes to obtain the dry mass (Wf). The supported amount (Ws) of the plaster was determined by the following formula.
Stucco loading Ws (mg/cm 2 ) = (Wfs-Wf)/100
繊維シートに担持された漆喰の抽出粒子径；
　１００ｍｍ×１００ｍｍサイズの漆喰処理繊維シートを５ｍｍ×５ｍｍのサイズに刻んで、トルエン中でスターラーにて３時間攪拌した後、繊維シートを取り出した。残ったトルエン溶液を静置して沈降した漆喰を分離し、繰り返しトルエンで洗浄してアクリル分を除去した後、乾燥させて粉体状の漆喰を抽出した。
　抽出した漆喰は、水を加えてアルミナルツボで１次粒子へ分散させた後、ＪＩＳ　Ｚ　８８２５に準拠し、水溶媒にてレーザー回折法を用いて粒度分布を測定し、得られたモード径をもって抽出粒子径（μｍ）とした。 Extraction particle size of the stucco carried on the fiber sheet;
A plaster-treated fiber sheet having a size of 100 mm×100 mm was cut into a size of 5 mm×5 mm, stirred in toluene with a stirrer for 3 hours, and then the fiber sheet was taken out. The remaining toluene solution was allowed to stand to separate the sedimented plaster, which was repeatedly washed with toluene to remove the acrylic content, and then dried to extract powdery plaster.
After adding water to the extracted plaster and dispersing it into primary particles in an alumina crucible, the particle size distribution was measured using a laser diffraction method with a water solvent in accordance with JIS Z 8825, and the mode diameter obtained was It was taken as the extracted particle size (μm).
全細孔容積；
　１００ｍｍ×１００ｍｍサイズの漆喰処理繊維シートを１ｍｍ×５ｍｍのサイズに刻んだ後、ＪＩＳ　Ｚ　８８３１に準拠し、窒素ガス吸着法を用いて同繊維シートの全細孔容積（Ｐｆｓ）を測定した。さらに、漆喰質量に対する全細孔容積（Ｐｓ）を以下の計算式で求めた。尚、不織布のみの全細孔容積Ｐｓは、測定限界以下であった。
　　漆喰の全細孔容積Ｐｓ（ｃｍ３／ｇ）＝Ｐｆｓ×（Ｗｆｓ－Ｗｆ）／Ｗｆｓ total pore volume;
A 100 mm×100 mm size plaster-treated fiber sheet was cut into 1 mm×5 mm sizes, and then the total pore volume (Pfs) of the same fiber sheet was measured using a nitrogen gas adsorption method according to JIS Z 8831. Furthermore, the total pore volume (Ps) with respect to the plaster mass was determined by the following formula. The total pore volume Ps of only the nonwoven fabric was below the measurement limit.
Total pore volume of stucco Ps (cm 3 /g) = Pfs × (Wfs - Wf) / Wfs
含水率；
　Ｎ９５マスク（デルタプラス社製）を用い、オリジナルの表層不織布の一部を３０×６０ｍｍのサイズで剥し取り、同個所に対して同じサイズの漆喰担持繊維シートを２体切断し、１体の質量（Ｗ０１）を測定した後、剥し取った表層不織布の部位へ縫付け性能評価マスクとした。もう１体は質量（Ｗ０２）を測定した後、１００℃×１０分間乾燥させて質量（ＷＤ２）を測定した。
　得られた性能評価マスクを人体に装着し、４時間後、８時間後に縫付けた同繊維シートを外して質量（Ｗ４，Ｗ８）及びアルカリ活性を測定した。マスクを装着したｎ時間毎の含水率（Ｍｎ）は、夫々の時間毎に測定した質量（Ｗｎ）を用いて、下記式より算出した。
　　　含水率（％）＝〔（Ｗｎ‐Ｗ０１）／Ｗ０１＋（Ｗ０２‐ＷＤ２）／ＷＤ２］／１００
　また、下記式より、８時間平均含水率を得た。
　　　８時間平均含水率（％）＝（Ｍ０＋Ｍ４＋Ｍ８）／３ moisture content;
Using an N95 mask (manufactured by Delta Plus), part of the original surface layer non-woven fabric was peeled off in a size of 30 x 60 mm, and two plaster-supporting fiber sheets of the same size were cut at the same location. After measuring (W 01 ), it was used as a sewing performance evaluation mask on the part of the peeled surface layer nonwoven fabric. After measuring the mass (W 02 ) of the other body, it was dried at 100° C. for 10 minutes and the mass (W D2 ) was measured.
The obtained performance evaluation mask was worn on the human body, and after 4 hours and 8 hours, the sewn same fiber sheet was removed, and the mass (W 4 , W 8 ) and alkaline activity were measured. The moisture content (M n ) for each n hours of wearing the mask was calculated from the following formula using the mass (W n ) measured for each hour.
Water content (%) = [(W n - W 01 )/W 01 + (W 02 - W D2 )/W D2 ]/100
Also, the 8-hour average moisture content was obtained from the following formula.
8-hour average moisture content (%) = (M 0 + M 4 + M 8 )/3
アルカリ活性；
　性能評価マスクに縫付けた漆喰処理繊維シートを４時間後、８時間後に剥し取り、［００３８］の質量を測定した後、以下の方法でアルカリ活性を判定した。
　水中に５秒間浸漬したｐＨ試験紙を漆喰処理不織布の表面に４秒間指でしっかり密着させ、得られた同紙の発色とｐＨ基準色を照らしてｐＨ値を判定した。尚、マスク装着前の０時間では全ての実験例共にアルカリ判定１２．５であった。
　ｐＨ試験紙としては、０．５刻みで読み取りできるｐＨ試験紙（ＩａｉｎＳｔａｒｓ　Ｓｈｏｐ－Ａｍａｚｏｎ）を用いた。
　また、先に説明した原理に沿って、呼吸周期毎に発生する吐息からの断続的な水分供給に対するアルカリ活性評価を目的に４秒間加水してｐＨ試験紙の発色を判定した。
　尚、４秒間の加水によるアルカリ活性判定試験は、先に説明した原理に沿って、呼吸周期毎に発生する吐息からの断続的な水分供給によるアルカリ活性の再現を目的とする。 alkaline activity;
After 4 hours and 8 hours, the plaster-treated fiber sheet sewn on the performance evaluation mask was peeled off, the mass of [0038] was measured, and alkali activity was determined by the following method.
A pH test paper was immersed in water for 5 seconds and then firmly attached to the surface of the plaster-treated nonwoven fabric for 4 seconds. At 0 hours before wearing the mask, the alkali judgment was 12.5 in all experimental examples.
As the pH test paper, pH test paper (IainStars Shop-Amazon) that can be read in increments of 0.5 was used.
In addition, according to the principle described above, water was added for 4 seconds to determine the color development of the pH test paper for the purpose of evaluating the alkaline activity against the intermittent water supply from exhalation occurring in each respiratory cycle.
The alkaline activity determination test by adding water for 4 seconds aims at reproducing the alkaline activity by intermittent water supply from the exhaled breath occurring in each respiratory cycle, in line with the principle described above.
不織布；
　下記表１に示す繊維シートを実験に用いた。
Figure JPOXMLDOC01-appb-T000001
 non-woven;
The fiber sheets shown in Table 1 below were used in the experiment.
Figure JPOXMLDOC01-appb-T000001
消石灰；
　実験に用いた消石灰としては、以下の表２に示す仕様のものを用いた。
Figure JPOXMLDOC01-appb-T000002
 slaked lime;
As the slaked lime used in the experiment, those having specifications shown in Table 2 below were used.
Figure JPOXMLDOC01-appb-T000002
＜実験例１＞
　表１に記載した１００ｍｍ×１００ｍｍサイズの不織布ＮＷ１に対して、表２記載の消石灰（ＳＬ３）を使用し、表３の配合で消石灰及び溶媒等を容器に入れてスターラーにより５分間撹拌し、得られた消石灰含有混合液をディッピング法により含侵塗布した後、２０℃、６０％ＲＨの室内で１２時間放置し、漆喰処理繊維シートを得た。尚、アクリル樹脂としてはポリトロンＡ５４００（（株）旭化成製）を用いた。
　得られた漆喰処理繊維シートを用いて、含水率及びアルカリ活性の測定を行い、得られた結果を表４に示す。 <Experimental example 1>
For the 100 mm × 100 mm size nonwoven fabric NW1 described in Table 1, use the slaked lime (SL3) described in Table 2, put the slaked lime and solvent, etc. in a container with the composition of Table 3, and stir with a stirrer for 5 minutes to obtain. After impregnating and applying the mixed liquid containing slaked lime by dipping, it was allowed to stand in a room at 20° C. and 60% RH for 12 hours to obtain a stucco-treated fiber sheet. Polytron A5400 (manufactured by Asahi Kasei Corp.) was used as the acrylic resin.
Using the obtained plaster-treated fiber sheet, the moisture content and alkali activity were measured, and Table 4 shows the results obtained.
＜実験例２～４＞
　実験例１の水量及びＩＰＡ（イソプロパノール）量を表３のように変更した以外は、実験例１と同様にして調製された消石灰含有混合液をディッピング法により含侵塗布し、漆喰担持繊維シートを得た。
　さらに、実験例１と同様にして性能評価マスク得た。得られた含水率及びアルカリ活性の試験結果を表４に示す。尚、実験例１と３のみ、図５のデータ補完を目的にマスク装着時間２時間及び６時間の含水率を測定した。 <Experimental Examples 2 to 4>
Except that the amount of water and the amount of IPA (isopropanol) in Experimental Example 1 were changed as shown in Table 3, a mixed solution containing slaked lime prepared in the same manner as in Experimental Example 1 was impregnated and applied by a dipping method to form a stucco-supporting fiber sheet. Obtained.
Further, a performance evaluation mask was obtained in the same manner as in Experimental Example 1. Table 4 shows the obtained water content and alkaline activity test results. Only in Experimental Examples 1 and 3, the water content was measured for 2 hours and 6 hours of wearing the mask for the purpose of supplementing the data in FIG.
＜実験例５～８＞
　実験例３で用いた消石灰ＳＬ３（Ｄ５０粒子径８μｍ）を、表３に示す消石灰に変えて調製された消石灰含有混合液をディッピング法により含侵塗布して漆喰担持繊維シートを得た。さらに、実験例１と同様にして性能評価マスク得た。得られた含水率及びアルカリ活性の試験結果を表４に示す。 <Experimental Examples 5 to 8>
Slaked lime SL3 (D50 particle diameter: 8 μm) used in Experimental Example 3 was replaced with the slaked lime shown in Table 3, and a mixed solution containing slaked lime was impregnated and coated by a dipping method to obtain a stucco-supporting fiber sheet. Further, a performance evaluation mask was obtained in the same manner as in Experimental Example 1. Table 4 shows the obtained water content and alkaline activity test results.
＜実験例９、１０＞
　実験例３での漆喰担持量を表３に示す数値に変更して調製された消石灰含有混合液をディッピング法により含侵塗布して漆喰担持繊維シートを得た。さらに、実験例１と同様にして性能評価マスク得た。得られた含水率及びアルカリ活性の試験結果を表４に示す。 <Experimental Examples 9 and 10>
A plaster-carrying fiber sheet was obtained by impregnating and applying a mixed solution containing slaked lime prepared by changing the plaster-carrying amount in Experimental Example 3 to the values shown in Table 3 by a dipping method. Further, a performance evaluation mask was obtained in the same manner as in Experimental Example 1. Table 4 shows the obtained water content and alkaline activity test results.
＜実験例１１＞
　実験例３で用いた繊維シート（不織布ＮＷ１）を織布ＮＷ２に変更し、漆喰担持量を表３に記載の数値に変更して漆喰担持繊維シートを得た。さらに、実験例１と同様にして性能評価マスク得た。得られた含水率及びアルカリ活性の試験結果を表４に示す。 <Experimental example 11>
The fiber sheet (non-woven fabric NW1) used in Experimental Example 3 was changed to the woven fabric NW2, and the amount of plaster supported was changed to the value shown in Table 3 to obtain a plaster-supported fiber sheet. Further, a performance evaluation mask was obtained in the same manner as in Experimental Example 1. Table 4 shows the obtained water content and alkaline activity test results.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
　上述した実験結果は、図２～図９にも示した。 The above experimental results are also shown in Figures 2 to 9.
＜実験例１２＞
　不織布マスクであるバリエールブロック（（有）大志製，特許文献１の抗ウイルス剤を使ったフィルターを使用）を用いて、４層ある不織布の中で外側から２層目のウイルス対策フィルターを取り出した。実験例１の漆喰処理繊維シートの代わりに同対策フィルターを用いた以外は同様にして性能評価マスクを得た。
　得られた測定結果は、抽出粒子径；１．２μｍ、細孔容積；０．２０２、マスク装着後のアルカリ活性０時間後；ｐＨ１２．５、４時間後；ｐＨ１１．０、８時間後；ｐＨ９．０であった。
　８時間経過後では、ｐＨが大きく低下し、アルカリ活性（抗ウイルス性）が不満足となっていることが判る。 <Experimental example 12>
Using a non-woven fabric mask Barrière Block (manufactured by Taishi Co., Ltd., using a filter using the antiviral agent of Patent Document 1), the second anti-virus filter was removed from the outside of the four layers of non-woven fabric. . A performance evaluation mask was obtained in the same manner as in Experimental Example 1, except that the plaster-treated fiber sheet was replaced with the same countermeasure filter.
The measurement results obtained are: extracted particle diameter: 1.2 μm, pore volume: 0.202, alkali activity after 0 hours after wearing the mask: pH 12.5, 4 hours later: pH 11.0, 8 hours later: pH 9 .0.
After 8 hours, the pH decreased significantly, indicating that the alkaline activity (antiviral properties) was unsatisfactory.
　　　１：繊維シート
　　　３：ウイルス
  1: fiber sheet 3: virus

Claims (8)

  1. 　漆喰が表面に担持されている繊維シートからなる抗ウイルス性シート。 An antiviral sheet consisting of a fiber sheet with plaster carried on the surface.
  2. 　前記繊維シートが不織布である請求項１に記載の抗ウイルス性シート。 The antiviral sheet according to claim 1, wherein the fiber sheet is a nonwoven fabric.
  3. 　前記不織布がポリオレフィン製である請求項２に記載の抗ウイルス性シート。 The antiviral sheet according to claim 2, wherein the nonwoven fabric is made of polyolefin.
  4. 　前記不織布が親水性繊維からなる請求項２に記載の抗ウイルス性シート。 The antiviral sheet according to claim 2, wherein the nonwoven fabric is made of hydrophilic fibers.
  5. 　窒素法で測定した全細孔容積が０．０２６～０．０６ｃｍ３／ｇの範囲にある請求項２に記載の抗ウイルス性シート。 3. The antiviral sheet according to claim 2, wherein the total pore volume measured by the nitrogen method is in the range of 0.026-0.06 cm 3 /g.
  6. 　前記繊維シートに担持されている漆喰を溶剤抽出し、レーザー回折法で測定した抽出粒子径が２～４０μｍの範囲にある請求項１に記載の抗ウイルス性シート。 The antiviral sheet according to claim 1, wherein the plaster carried on the fiber sheet is subjected to solvent extraction, and the extracted particle size measured by a laser diffraction method is in the range of 2 to 40 μm.
  7. 　漆喰の担持量が１．４～４．０ｍｇ／ｃｍ２の範囲にある請求項１に記載の抗ウイルスシート。 The antiviral sheet according to claim 1, wherein the amount of plaster carried is in the range of 1.4 to 4.0 mg/cm 2 .
  8. 　マスク或いは防護服に適用される請求項１に記載の抗ウイルス性シート。
          The antiviral sheet according to claim 1, which is applied to masks or protective clothing.
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Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005013695A1 (en) * 2003-08-12 2005-02-17 Mochigase Electrical Equipment Co., Ltd. Antiviral agent and fibers and antiviral members using the same
JP2007075432A (en) * 2005-09-15 2007-03-29 Tokuyama Corp Deodorization sheet and deodorization method
JP2010209490A (en) * 2009-03-10 2010-09-24 Clear Office Kk Antimicrobial fiber, antimicrobial filter, and method for producing the same
JP2011057844A (en) * 2009-09-10 2011-03-24 Himeno Innovec Kk Aqueous composition that forms flexible film
JP2012096981A (en) * 2010-10-06 2012-05-24 Tottori Univ Raw material for antiviral coating material composition, antiviral coating material composition, and method for producing the composition
JP2012158841A (en) * 2011-01-31 2012-08-23 Suzukura Industry Inc Polyester-based fiber fabric coated with plaster
JP2012250422A (en) * 2011-06-02 2012-12-20 Tokuyama Corp Laminated sheet with plaster layer
JP2019055487A (en) * 2017-09-19 2019-04-11 東京カラーグラビヤ工業株式会社 Plaster sheet
JP2021176997A (en) * 2020-05-06 2021-11-11 株式会社アンジコア Plaster sheet and method for producing plaster coating yarn
JP2021177018A (en) * 2020-04-30 2021-11-11 日榮新化株式会社 mask
JP2022046875A (en) * 2020-09-11 2022-03-24 株式会社トクヤマ Antiviral fiber molding
JP2022050798A (en) * 2020-09-18 2022-03-31 株式会社トクヤマ Anti-virus non-woven fabric and anti-virus mask using the same

Patent Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005013695A1 (en) * 2003-08-12 2005-02-17 Mochigase Electrical Equipment Co., Ltd. Antiviral agent and fibers and antiviral members using the same
JP2007075432A (en) * 2005-09-15 2007-03-29 Tokuyama Corp Deodorization sheet and deodorization method
JP2010209490A (en) * 2009-03-10 2010-09-24 Clear Office Kk Antimicrobial fiber, antimicrobial filter, and method for producing the same
JP2011057844A (en) * 2009-09-10 2011-03-24 Himeno Innovec Kk Aqueous composition that forms flexible film
JP2012096981A (en) * 2010-10-06 2012-05-24 Tottori Univ Raw material for antiviral coating material composition, antiviral coating material composition, and method for producing the composition
JP2012158841A (en) * 2011-01-31 2012-08-23 Suzukura Industry Inc Polyester-based fiber fabric coated with plaster
JP2012250422A (en) * 2011-06-02 2012-12-20 Tokuyama Corp Laminated sheet with plaster layer
JP2019055487A (en) * 2017-09-19 2019-04-11 東京カラーグラビヤ工業株式会社 Plaster sheet
JP2021177018A (en) * 2020-04-30 2021-11-11 日榮新化株式会社 mask
JP2021176997A (en) * 2020-05-06 2021-11-11 株式会社アンジコア Plaster sheet and method for producing plaster coating yarn
JP2022046875A (en) * 2020-09-11 2022-03-24 株式会社トクヤマ Antiviral fiber molding
JP2022050798A (en) * 2020-09-18 2022-03-31 株式会社トクヤマ Anti-virus non-woven fabric and anti-virus mask using the same

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