WO2022196393A1 - Feuille antivirale - Google Patents

Feuille antivirale 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
Authority
WO
WIPO (PCT)
Prior art keywords
plaster
fiber sheet
antiviral
mask
sheet
Prior art date
Application number
PCT/JP2022/009412
Other languages
English (en)
Japanese (ja)
Inventor
正 藤本
浩喜 平山
Original Assignee
株式会社トクヤマ
正 藤本
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
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/fr

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Classifications

    • 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)
  • Respiratory Apparatuses And Protective Means (AREA)
  • Nonwoven Fabrics (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Laminated Bodies (AREA)
  • Medicinal Preparation (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)

Abstract

L'invention concerne une feuille antivirale qui comprend une feuille en fibre contenant du plâtre.
PCT/JP2022/009412 2021-03-17 2022-03-04 Feuille antivirale WO2022196393A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2021043525A JP2024065132A (ja) 2021-03-17 2021-03-17 抗ウイルス性シート
JP2021-043525 2021-03-17

Publications (1)

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WO2022196393A1 true WO2022196393A1 (fr) 2022-09-22

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TW (1) TW202300043A (fr)
WO (1) WO2022196393A1 (fr)

Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005013695A1 (fr) * 2003-08-12 2005-02-17 Mochigase Electrical Equipment Co., Ltd. Agent antiviral ainsi que fibres et elements antiviraux pourvus dudit agent
JP2007075432A (ja) * 2005-09-15 2007-03-29 Tokuyama Corp 脱臭シート及び脱臭方法。
JP2010209490A (ja) * 2009-03-10 2010-09-24 Clear Office Kk 抗菌性繊維、抗菌性フィルタおよび製造方法
JP2011057844A (ja) * 2009-09-10 2011-03-24 Himeno Innovec Kk 可撓性被膜を形成する水性組成物
JP2012096981A (ja) * 2010-10-06 2012-05-24 Tottori Univ 抗ウイルス性塗材組成物原料、抗ウイルス性塗材組成物及びその製造方法
JP2012158841A (ja) * 2011-01-31 2012-08-23 Suzukura Industry Inc 漆喰が塗工されてなるポリエステル系繊維布帛
JP2012250422A (ja) * 2011-06-02 2012-12-20 Tokuyama Corp 漆喰層を有する積層シート
JP2019055487A (ja) * 2017-09-19 2019-04-11 東京カラーグラビヤ工業株式会社 漆喰シート
JP2021176997A (ja) * 2020-05-06 2021-11-11 株式会社アンジコア 漆喰シート及び漆喰塗膜糸の製造方法
JP2021177018A (ja) * 2020-04-30 2021-11-11 日榮新化株式会社 マスク
JP2022046875A (ja) * 2020-09-11 2022-03-24 株式会社トクヤマ 抗ウイルス性繊維成形体
JP2022050798A (ja) * 2020-09-18 2022-03-31 株式会社トクヤマ 抗ウイルス性不織布、及びこれを用いた抗ウイルス性マスク

Patent Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005013695A1 (fr) * 2003-08-12 2005-02-17 Mochigase Electrical Equipment Co., Ltd. Agent antiviral ainsi que fibres et elements antiviraux pourvus dudit agent
JP2007075432A (ja) * 2005-09-15 2007-03-29 Tokuyama Corp 脱臭シート及び脱臭方法。
JP2010209490A (ja) * 2009-03-10 2010-09-24 Clear Office Kk 抗菌性繊維、抗菌性フィルタおよび製造方法
JP2011057844A (ja) * 2009-09-10 2011-03-24 Himeno Innovec Kk 可撓性被膜を形成する水性組成物
JP2012096981A (ja) * 2010-10-06 2012-05-24 Tottori Univ 抗ウイルス性塗材組成物原料、抗ウイルス性塗材組成物及びその製造方法
JP2012158841A (ja) * 2011-01-31 2012-08-23 Suzukura Industry Inc 漆喰が塗工されてなるポリエステル系繊維布帛
JP2012250422A (ja) * 2011-06-02 2012-12-20 Tokuyama Corp 漆喰層を有する積層シート
JP2019055487A (ja) * 2017-09-19 2019-04-11 東京カラーグラビヤ工業株式会社 漆喰シート
JP2021177018A (ja) * 2020-04-30 2021-11-11 日榮新化株式会社 マスク
JP2021176997A (ja) * 2020-05-06 2021-11-11 株式会社アンジコア 漆喰シート及び漆喰塗膜糸の製造方法
JP2022046875A (ja) * 2020-09-11 2022-03-24 株式会社トクヤマ 抗ウイルス性繊維成形体
JP2022050798A (ja) * 2020-09-18 2022-03-31 株式会社トクヤマ 抗ウイルス性不織布、及びこれを用いた抗ウイルス性マスク

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JP2024065132A (ja) 2024-05-15
TW202300043A (zh) 2023-01-01

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