WO2021070566A1 - Feuille contenant du carbone non cristallin, produit en feuille contenant du carbone non cristallin et procédé pour conférer une propriété antimicrobienne ou une propriété anti-virale à une feuille perméable aux gaz - Google Patents

Feuille contenant du carbone non cristallin, produit en feuille contenant du carbone non cristallin et procédé pour conférer une propriété antimicrobienne ou une propriété anti-virale à une feuille perméable aux gaz Download PDF

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WO2021070566A1
WO2021070566A1 PCT/JP2020/034661 JP2020034661W WO2021070566A1 WO 2021070566 A1 WO2021070566 A1 WO 2021070566A1 JP 2020034661 W JP2020034661 W JP 2020034661W WO 2021070566 A1 WO2021070566 A1 WO 2021070566A1
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amorphous carbon
sheet
cloth
containing sheet
gas
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PCT/JP2020/034661
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English (en)
Japanese (ja)
Inventor
健二 平栗
修 小野寺
慶春 内海
祥和 田中
慎也 藤井
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学校法人東京電機大学
日本アイ・ティ・エフ株式会社
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Priority to JP2021550550A priority Critical patent/JP7436973B2/ja
Publication of WO2021070566A1 publication Critical patent/WO2021070566A1/fr

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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2/00—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor
    • A61L2/16—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor using chemical substances
    • A61L2/23—Solid substances, e.g. granules, powders, blocks, tablets
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/26—Deposition of carbon only
    • C23C16/27—Diamond only
    • 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
    • D06M11/73—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 carbon or compounds thereof
    • D06M11/74—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 carbon or compounds thereof with carbon or graphite; with carbides; with graphitic acids or their salts

Definitions

  • the present invention provides an amorphous carbon-containing sheet and an amorphous carbon-containing sheet product having antibacterial activity (hereinafter, also referred to as "antibacterial property") or antiviral property, and an antibacterial or antiviral property to a breathable sheet. Regarding the method of granting.
  • DLC diamond-like carbon
  • Patent Document 1 discloses a medical device such as an implant material having antibacterial properties and osteoconductivity by providing a DLC film on the surface of a base material.
  • Patent Document 2 discloses a DLC-fixed base material in which DLC is fixed on the surface of a sheet-shaped base material.
  • the DLC film is laminated on a base material made of a metal such as a titanium alloy and stainless steel, and has a nanoindentation hardness of 2000 MPa or more. ..
  • a DLC film having such high hardness is laminated on a flexible base material such as cloth, the film may crack and peel off from the surface of the base material.
  • Patent Document 1 only the antibacterial property of the DLC membrane against Staphylococcus aureus and Escherichia coli has been confirmed, and the antibacterial property against other bacteria is unknown.
  • the film formation of the DLC film is performed by a method of applying a high bias voltage of about ⁇ 2.5 kV to the base material by using a plasma CVD method or the like.
  • this method raises the temperature of the base material by ionic impact, the fibers may melt or burn when applied to a base material such as cloth.
  • Patent Document 2 uses cloth or the like as the base material.
  • Patent Document 2 does not disclose any specific method and conditions for fixing the DLC to the base material, and nothing has been demonstrated regarding the effect of the fixed base material. Therefore, it is difficult for a person skilled in the art to attempt to fix the DLC film to a base material such as cloth based on the disclosure of Patent Document 2.
  • the present invention has been made in view of the above problems, and an object thereof is an amorphous carbon-containing sheet having antibacterial or antiviral properties, an amorphous carbon-containing sheet product, and an antibacterial property for a breathable sheet. Alternatively, it is to provide a method for imparting antiviral properties.
  • the present inventors have succeeded in adhering amorphous carbon onto a (flexible) substrate having breathability and flexibility without peeling.
  • the amorphous carbon-containing sheet thus obtained has been found to have high antibacterial and antiviral properties, and has completed the present invention.
  • the present invention includes the following inventions.
  • the antibacterial activity value measured according to the JIS-L-1902: 2015 bacterial solution absorption method after 20 times of high-pressure steam sterilization treatment at 126 ° C. for 15 minutes is 4 or more (1).
  • An amorphous carbon-containing sheet product which is a sanitary product or a medical product having the amorphous carbon-containing sheet according to any one of (1) to (9) above.
  • (11) A method of imparting antibacterial properties to the breathable sheet by adhering amorphous carbon to at least a part of the breathable sheet.
  • (12) A method of imparting antiviral properties to the breathable sheet by adhering amorphous carbon to at least a part of the breathable sheet.
  • an amorphous carbon-containing sheet and an amorphous carbon-containing sheet product having antibacterial or antiviral properties and a method for imparting antibacterial or antiviral properties to a breathable sheet. can do.
  • the amorphous carbon-containing sheet is also excellent in abrasion resistance and oxidation resistance.
  • 6 is an SEM image showing the surfaces of a cotton cloth and the amorphous carbon-containing cloths of Examples 1 and 2 at a magnification of 100 times (upper row) and a magnification of 500 times (lower row).
  • 6 is an SEM image showing the surface of a cotton cloth at a magnification of 1000 times.
  • 6 is an SEM image showing the surface of the amorphous carbon-containing cloth of Example 1 at a magnification of 1000 times.
  • 6 is an SEM image showing the surface of the amorphous carbon-containing cloth of Example 2 at a magnification of 1000 times.
  • FIG. 6 is a photomicrograph of the surfaces of a cotton cloth and the amorphous carbon-containing cloths of Examples 1 and 2 observed with a microscope. It is a schematic block diagram which shows an example of the structure of the manufacturing apparatus which can be used for manufacturing the amorphous carbon-containing cloth which concerns on one aspect of this invention. It is a schematic block diagram which shows an example of the structure of the film forming apparatus which can be used for manufacturing the amorphous carbon-containing cloth which concerns on one aspect of this invention.
  • antibacterial means suppressing the growth of fungi such as bacteria and molds, or killing bacteria and fungi.
  • having antibacterial property means that the antibacterial activity value measured in accordance with the Japanese Industrial Standards (JIS) -L-1902: 2015 bacterial solution absorption method is 2 or more.
  • antiviral refers to inactivating a virus. Further, “having antiviral property” means that the antiviral activity value Mv measured in accordance with JIS-L-1922: 2016 is 2.0 or more.
  • the amorphous carbon-containing sheet according to one aspect of the present invention is formed by adhering amorphous carbon to at least a part of a breathable sheet as a base material.
  • the "amorphous carbon-containing sheet according to one aspect of the present invention” may be simply referred to as “the present amorphous carbon-containing sheet”.
  • the breathable sheet used as the base material is a breathable sheet-like member.
  • the breathable sheet is preferably flexible from the viewpoint of application to various specific applications.
  • the manufacturing method and raw materials thereof are not limited. Examples of such a breathable sheet include a cloth obtained by processing a plurality of fibers into a sheet and a porous sheet. Examples of the cloth include woven cloth, non-woven fabric, lace, felt and knitted cloth (knitted fabric).
  • the breathable sheet has a plurality of voids or pores through which a gas can pass.
  • the amorphous carbon-containing sheet exhibits suitable breathability according to the application such as hygiene products or medical products, and is antibacterial according to the application. It is possible to express sex and antiviral properties.
  • the breathability of the breathable sheet can be appropriately determined from the viewpoint that the amorphous carbon-containing sheet sufficiently expresses the inactivation of bacteria or viruses.
  • the inactivation of bacteria or viruses in the amorphous carbon-containing sheet can be appropriately determined according to the use of the amorphous carbon-containing sheet.
  • the air permeability of the breathable sheet is preferably small, and from the viewpoint of achieving a sufficiently large amount of air permeability and suppressing an increase in pressure loss due to air permeability, the air permeability of the breathable sheet. Is preferably large.
  • the breathable sheet is also determined according to the use of the amorphous carbon-containing sheet. From these viewpoints, the breathability of the breathable sheet can be appropriately determined from the range of 1 to 500 cm 3 / cm 2 seconds.
  • the "breathability" can be determined, for example, as the air permeability in the thickness direction of the breathable sheet in accordance with the breathability measurement method A defined in JIS-L-1096: 2010.
  • the fibers that make up the above cloth are not limited.
  • the fibers include plant fibers such as cotton and hemp; animal fibers such as silk and wool; regenerated fibers such as rayon and cupra; semi-synthetic fibers such as acetate and triacetate; polyamide (nylon), polyester and polyacrylic, Synthetic fibers such as polyurethane and polystyrene; or fibers obtained by blending these; metal fibers; ceramic fibers; and the like can be mentioned.
  • the above porous sheet is not limited.
  • the porous sheet include a sheet made of a resin such as polyurethane, which is made porous by a known method such as foaming, stretching, or perforation.
  • a cotton cloth woven with cotton as the breathable sheet because it exhibits particularly high antibacterial and antiviral properties by adhering amorphous carbon.
  • the thickness of the fiber is not limited, but it is desirable that the average fiber diameter is 1 ⁇ m or more and 100 ⁇ m or less from the viewpoint of exhibiting processability and sufficient flexibility as a sheet.
  • the thickness of the breathable sheet is not limited and may be appropriately determined from the viewpoint of application and desired breathability.
  • the surface of the breathable sheet may be subjected to an arbitrary pretreatment before adhering the amorphous carbon in order to enhance the bond with the amorphous carbon.
  • the surface of the breathable sheet is composed of a group consisting of a pretreatment gas, for example, a fluorine (F) -containing gas, a hydrogen (H) gas, an oxygen (O) gas, and an argon (Ar). Treatments such as exposure to plasma of at least one selected pretreatment gas may be mentioned.
  • fluorine (F) -containing gas examples include fluorine (F 2 ) gas, nitrogen trifluoride (NF 3 ) gas, sulfur hexafluoride (SF 6 ) gas, carbon tetrafluoride (CF 4 ) gas, and tetrafluoride.
  • fluorine (F 2 ) gas nitrogen trifluoride (NF 3 ) gas
  • sulfur hexafluoride (SF 6 ) gas sulfur hexafluoride (SF 6 ) gas
  • carbon tetrafluoride (CF 4 ) gas examples of the fluorine (F) -containing gas
  • fluorine (F) -containing gas examples include fluorine (F 2 ) gas, nitrogen trifluoride (NF 3 ) gas, sulfur hexafluoride (SF 6 ) gas, carbon tetrafluoride (CF 4 ) gas, and tetrafluoride.
  • silicon (SiF 4 ) gas silicon tetrafluoride (Si 2 F 6
  • the surface of the breathable sheet can be cleaned and the adhesion between the breathable sheet and the amorphous carbon can be improved.
  • hydrogen gas or oxygen gas as the pretreatment gas, it is possible to efficiently remove stains such as organic substances adhering to the surface of the breathable sheet.
  • the surface of the breathable sheet is made to be fluorine-terminated or hydrogen-terminated. Therefore, when amorphous carbon is attached to the surface, the fluorine atom or hydrogen atom on the surface of the breathable sheet and the carbon atom of the amorphous carbon form a fluorine-carbon bond or a hydrogen-carbon bond. Adhesion between the breathable sheet and amorphous carbon is improved.
  • the pretreatment with the plasma may be performed once or a plurality of times using one type of pretreatment gas, or may be performed a plurality of times using two or more types of pretreatment gas.
  • the breathable sheet may be exposed to an oxygen gas plasma and then a fluorine-containing gas plasma or a hydrogen gas plasma. As a result, the adhesion between the breathable sheet and the amorphous carbon becomes particularly good.
  • the amorphous carbon constituting the present amorphous carbon-containing sheet adheres to the (flexible) substrate having breathability and flexibility without peeling.
  • the amorphous carbon may be so-called diamond-like carbon (DLC), or may be a composition having a hardness lower than that of DLC.
  • the amorphous carbon may contain an element other than carbon, for example, fluorine, if necessary.
  • the amorphous carbon may be attached to at least a part of the surface of the breathable sheet.
  • Amorphous carbon adheres so as to cover at least a part of the surface of the breathable sheet without filling the voids or pores of the breathable sheet from the viewpoint of exhibiting sufficient antibacterial and antiviral properties.
  • the base material is a cloth
  • the fibers constituting the cloth are adhered so as to cover at least a part of the surface of the fibers without binding them, that is, without filling the gaps between the fibers.
  • Such a configuration can also be rephrased as flexible amorphous carbon coated on the fiber.
  • the flexibility of the breathable sheet is impaired when the amorphous carbon film is laminated on the surface of the breathable sheet. Also, cracking and peeling of the amorphous carbon film may occur.
  • the obtained amorphous carbon-containing sheet is a breathable sheet. More preferably expresses the deformability of.
  • the base material is cloth
  • amorphous carbon is attached so as to cover at least a part of the surface of the fiber, it adheres to the fiber constituting the flexible cloth, and the movement (deformation) of the fiber is performed.
  • the present amorphous carbon-containing sheet can retain the flexibility originally possessed by the breathable sheet as a base material, and the amorphous carbon is difficult to peel off from the breathable sheet. ..
  • the amorphous carbon By adhering the amorphous carbon to at least a part of the base material breathable sheet so as to cover at least a part of the surface of the fiber without filling the voids or pores between the fibers, for example.
  • the amorphous carbon is more difficult to peel off from the surface of the breathable sheet.
  • This amorphous carbon-containing sheet exhibits higher antibacterial and antiviral properties, and also has oxidation resistance, and the antibacterial and antiviral properties are less likely to decrease even after repeated high-pressure steam sterilization treatments. ..
  • the amount of amorphous carbon adhering to the breathable sheet can be appropriately set according to the properties and use of the breathable sheet.
  • the amount of adhesion may be appropriately set so that the amorphous carbon does not fill the voids between the fibers and bond the fibers to each other, or is appropriately set within a range in which air permeability by the pores can be obtained. May be done.
  • the amorphous carbon contains fluorine. Since the amorphous carbon contains fluorine, it exhibits higher antibacterial and antiviral properties against anaerobic bacteria, aerobic bacteria and viruses, and also improves oxidation resistance, and repeats high-pressure steam sterilization treatment. High antibacterial and antiviral properties can be maintained after application. This is because the amorphous carbon contains fluorine, so that a carbon-fluorine bond with high bonding strength is formed in the amorphous carbon, and it is difficult to form a carbon-oxygen bond even if the high-pressure steam sterilization treatment is repeated. It is thought that this is because.
  • the fluorine content is preferably 0.1 at% or more, more preferably 10 at% or more, and preferably 25 at% or less, preferably 20 at. More preferably, it is less than%.
  • the fluorine content is in the above range, more remarkable antibacterial and antiviral properties can be reliably expressed.
  • the fluorine content is a numerical value obtained based on the atomic composition percentage of each element in amorphous carbon, which is measured by using the XPS (X-Ray Photoelectron Spectroscopy) method.
  • the above measurement is performed using a damage-free multi-plasma jet device (JPS-90100MC) manufactured by Plasma Concept Tokyo Co., Ltd. under the conditions of X-ray: MgK ⁇ ray, voltage: 10.0 kV, and current: 10 mA.
  • the amorphous carbon-containing sheet according to one aspect of the present invention has an antibacterial effect with respect to the antibacterial activity value measured in accordance with the JIS-L-1902: 2015 bacterial solution absorption method (corresponding to ISO 20743: 2013). It shows 2 or more, and depending on the bacterium, preferably 4 or more, more preferably 5 or more, further preferably 6 or more, and particularly preferably a numerical value equal to or higher than the upper limit of measurement.
  • this amorphous carbon-containing sheet has an antibacterial activity value measured in accordance with the JIS-L-1902: 2015 bacterial solution absorption method after being subjected to high-pressure steam sterilization treatment at 126 ° C. for 15 minutes 20 times. It shows 2 or more which is said to have an antibacterial effect, preferably 4 or more depending on the bacterium, more preferably 5 or more, further preferably 6 or more, and particularly preferably a numerical value equal to or higher than the upper limit of measurement. Shown.
  • the amorphous carbon-containing sheet has a particularly good antibacterial effect against anaerobic bacteria, particularly facultative anaerobic bacteria such as Escherichia coli and Staphylococcus aureus, and aerobic bacteria, particularly Salmonella and Klebsiella pneumoniae. Demonstrate.
  • the amorphous carbon-containing sheet can maintain a good antibacterial effect for a long period of time.
  • the amorphous carbon-containing sheet according to one aspect of the present invention has an antiviral activity value measured in accordance with an antiviral test method for textile products of JIS-L-1922: 2016 (corresponding to ISO 18184: 2019).
  • Mv it shows 2.0 or more, which is said to have an antiviral effect, preferably 3.0 or more depending on the virus, more preferably 4.0 or more, and particularly preferably a value above the upper limit of measurement. Shown.
  • this amorphous carbon-containing sheet has an antiviral activity value of Mv measured in accordance with JIS-L-1922: 2016 after being subjected to high-pressure steam sterilization treatment at 126 ° C. for 15 minutes 20 times. It shows 2.0 or more, which is said to have an antiviral effect, preferably 3.0 or more depending on the virus, more preferably 4.0 or more, and particularly preferably a numerical value of a measurement upper limit or more.
  • the amorphous carbon-containing sheet is a good antivirus against various viruses, for example, an enveloped virus such as influenza A virus (H3N2, H1N1) and a non-enveloped virus such as cat calicivirus. It is effective. In addition, the amorphous carbon-containing sheet can maintain a good antiviral effect for a long period of time.
  • an enveloped virus such as influenza A virus (H3N2, H1N1)
  • a non-enveloped virus such as cat calicivirus. It is effective.
  • the amorphous carbon-containing sheet can maintain a good antiviral effect for a long period of time.
  • the "compliance" with respect to the measurement of the present specification may be by the reference method itself, or by substantially the same method as the reference method.
  • “compliance” may mean converting the result of a method different from the reference method into the result of the reference method.
  • the amorphous carbon-containing sheet according to one aspect of the present invention is also excellent in wear resistance. Further, the amorphous carbon-containing sheet according to one aspect of the present invention preferably has a contact angle of 100 ° or more, more preferably 120 ° or more, on the surface thereof immediately after dropping pure water. .. Although the reason is unknown, the higher the contact angle is, the higher the amorphous carbon-containing sheet exhibits the higher antibacterial effect and antiviral effect.
  • the contact angle is measured by contacting a droplet of pure water with the amorphous carbon adhering surface of the test piece and measuring the angle formed by the sample surface and the liquid surface when the droplet is deposited. It is a numerical value obtained.
  • the contact angle can be controlled by controlling the amount of amorphous carbon adhered, the content of fluorine in the amorphous carbon, and the like.
  • the amorphous carbon-containing sheet is produced by forming amorphous carbon on the surface of a breathable sheet as a base material by a plasma CVD method, a sputtering method, or the like. It is preferable to use the plasma CVD method in that the pretreatment of the breathable sheet with plasma and the formation of amorphous carbon can be performed in the same manufacturing apparatus.
  • the plasma raw material gas includes a hydrocarbon gas, a hydrocarbon gas, and if necessary, a mixed gas in which hydrogen gas, an inert gas, etc. are mixed as a carrier gas. Can be mentioned.
  • the hydrocarbon gas is not particularly limited as long as it is a hydrocarbon gas capable of supplying carbon, and is, for example, methane (CH 4 ), ethane (C 2 H 6 ), propane (C 3 H 8 ), butane (C 3 H 8).
  • C 4 H 10 ), acetylene (C 2 H 2 ), benzene (C 6 H 6 ) and the like can be mentioned.
  • methane, ethane, acetylene and the like are preferable because they are inexpensive and easily available.
  • the fluorine carbide gas is not particularly limited as long as it can supply fluorine, but since it is inexpensive and easily available, carbon tetrafluoride (CF 4 ) and dicarbonate hexafluoride are available. (C 2 F 6 ) and the like can be mentioned.
  • FIG. 11 is a schematic block diagram showing an example of the configuration of a manufacturing apparatus that can be used for manufacturing an amorphous carbon-containing sheet according to an aspect of the present invention.
  • the manufacturing apparatus shown in FIG. 11 is a parallel plate type plasma CVD apparatus.
  • the device has a vacuum chamber 1 to which an exhaust device 11 is attached, and an electrode 2 and an electrode 3 are installed in the vacuum chamber 1 at a position facing the electrode 2.
  • the electrode 3 is grounded, and a high frequency power supply 23 is connected to the electrode 2 via a matching box 22.
  • the electrode 2 is provided with a base material holder for supporting the breathable sheet S1 which is a base material, and depending on the material of the breathable sheet, the breathable sheet S1 is provided during amorphous carbon formation. It is desirable that a cooling device such as a water cooling mechanism 21 for cooling is attached.
  • the vacuum chamber 1 is provided with a gas supply unit 4 so that the plasma raw material gas can be introduced inside.
  • the gas supply unit 4 is connected to the mass flow controllers 411, 412, ..., And one or more gas sources 431, 432 for supplying the plasma raw material gas connected via valves 421, 422, .... , ... are included.
  • the surface to be treated S1'of the breathable sheet S1 is arranged on the base material holder of the electrode 2 toward the facing electrode 3.
  • the exhaust device 11 is operated to bring the inside of the vacuum chamber 1 to a predetermined degree of vacuum.
  • one or more of fluorine-containing gas, hydrogen gas, and oxygen gas are introduced from the gas supply unit 4 into the vacuum chamber 1 as pretreatment gas, and the high-frequency power source 23 is introduced through the matching box 22. High-frequency power is supplied to the electrode 2.
  • the introduced pretreatment gas is turned into plasma, and the surface treatment (pretreatment) of the breathable sheet S1 is performed in the presence of this plasma. It should be noted that this surface treatment does not necessarily have to be performed.
  • the inside of the vacuum chamber 1 is evacuated again, and then the hydrocarbon gas and / or the fluorine carbide gas is introduced into the vacuum chamber 1 from the gas supply unit 4 as a plasma raw material gas, and the high frequency power supply 23 is used. Supply high frequency power to the electrode 2.
  • the concentration (supply amount) of the plasma raw material gas may be appropriately set according to the processing capacity of the manufacturing apparatus and the like, and is not particularly limited. As a result, the introduced plasma raw material gas is turned into plasma, and in the presence of this plasma, amorphous carbon is formed on the surface of the breathable sheet S1 (amorphous carbon forming step).
  • the fluorine content in the amorphous carbon is adjusted to a desired value by adjusting the mixing ratio of the hydrocarbon gas introduced as the plasma raw material gas and the fluorine hydrocarbon gas. Can be controlled.
  • FIG. 12 is a schematic block diagram showing an example of the configuration of a film forming apparatus that can be used for producing an amorphous carbon-containing sheet according to one aspect of the present invention.
  • the film forming apparatus shown in FIG. 12 is an inductively coupled plasma CVD apparatus.
  • the device has a vacuum container 1'attached with an exhaust device 11', and an induction coil electrode 5 is wound around the outer circumference of the vacuum container 1'.
  • a matching box 51 and a high-frequency power supply 52 are connected to both ends of the induction coil electrode 5.
  • a base material holder for supporting the breathable sheet S1 which is a base material is provided inside the vacuum container 1'. It is desirable that a cooling device such as a water cooling mechanism for cooling the breathable sheet S1 is provided inside the base material holder depending on the material of the breathable sheet.
  • the exhaust device 11' is connected to the vacuum vessel 1'by a pipe, and the gas supply unit 4'is also connected to the pipe so that the plasma raw material gas can be introduced inside.
  • the gas supply unit 4' is supplied with one or more plasma source gases connected via mass flow controllers 411', 412', ..., And valves 421', 422', .... Gas sources 431', 432', ...
  • the same amorphous carbon forming step as in the case of producing the present amorphous carbon-containing sheet using the manufacturing apparatus of FIG. 11 is performed. Do. However, in the film forming apparatus, the plasma raw material gas is converted into plasma by applying high frequency power to the induction coil electrode 5.
  • Amorphous carbon formation conditions When forming amorphous carbon by the plasma CVD method, the above-mentioned plasma raw material gas and manufacturing (deposition) apparatus are used, and various conditions in the amorphous carbon forming step are selected to ventilate the base material.
  • Amorphous carbon can be attached to at least a part of the surface of the breathable sheet without filling the voids or pores of the sex sheet.
  • the base material is cloth
  • amorphous carbon can be attached so as to cover at least a part of the surface of the fibers without binding the fibers constituting the cloth.
  • the pressure in the vacuum chamber is adjusted by introducing the plasma raw material gas into the vacuum chamber (vacuum chamber) of the plasma CVD apparatus.
  • the pressure in the vacuum chamber is preferably 0.1 Pa or more, and more preferably 1 Pa or more, from the viewpoint of increasing the film forming speed.
  • the pressure in the vacuum chamber is preferably 100 Pa or less, and more preferably 50 Pa or less. If the pressure in the vacuum chamber is within this range, there is an advantage that both a high film forming speed and a low temperature film forming can be achieved at the same time.
  • the applied power from the high-frequency power source that supplies power is preferably 100 W or more, and more preferably 200 W or more, from the viewpoint of increasing the film forming speed. Further, the applied power is preferably 800 W or less, and more preferably 600 W or less, from the viewpoint of preventing the base material temperature from rising. If the applied power is within this range, there is an advantage that both a high film forming speed and a low temperature film forming can be achieved at the same time.
  • the temperature of the breathable sheet as the base material is preferably maintained at 80 ° C. or lower, preferably 60 ° C. or lower, in consideration of the heat resistance of the material constituting the breathable sheet. It is more preferable to be done.
  • a method of keeping the temperature of the breathable sheet within this range in the formation of amorphous carbon, a method of cooling the base material holder for supporting the breathable sheet by a cooling device, and a method of applying a small applied power for a long time are used. Examples thereof include a method of suppressing a temperature rise of the breathable sheet by applying the coating.
  • the processing time can be appropriately set according to the processing capacity of the manufacturing (deposition) apparatus, the concentration (supply amount) of the plasma raw material gas, the amount of amorphous carbon adhering to the breathable sheet, and the like.
  • the amorphous carbon forms an amorphous carbon-containing sheet adhered so as to cover at least a part of the surface of the breathable sheet without filling the voids or pores of the breathable sheet. can do.
  • the base material is cloth
  • the nanoindentation hardness of the amorphous carbon is 5000 MPa or less for the amorphous carbon containing no fluorine when the amorphous carbon formed on the silicon wafer is measured at a load of 100 mg in the same manner. Yes, the amount of amorphous carbon containing fluorine is 1000 MPa or less. Therefore, the amorphous carbon itself has some flexibility.
  • Amorphous carbon-containing sheet products Since the amorphous carbon-containing sheet according to one aspect of the present invention exhibits high antibacterial and antiviral properties against various bacteria, fungi and viruses, it is an amorphous carbon-containing sheet for hygiene products or medical products. It is particularly preferably used as a product.
  • sanitary goods include, for example, masks, sanitary goods, diapers; bedding such as sheets, duvet covers, bedspreads, pillowcases, especially bedding used in hospitals; clothes, socks, underwear, various work clothes, surgery.
  • Clothing such as clothes, white clothes, pajamas (especially pajamas worn by patients in hospitals); cloth products such as hats, gloves, towels; etc. (products in which cloth is used at least in part), and cloth of the cloth products. Examples include, but are not limited to, porous sheet products in which some or all are replaced with porous sheets.
  • medical products include cloth products such as gauze, bandages, and adhesive plasters (products in which cloth is used in at least a part), and a part or all of the cloth of the cloth product is replaced with a porous sheet.
  • cloth products such as gauze, bandages, and adhesive plasters (products in which cloth is used in at least a part), and a part or all of the cloth of the cloth product is replaced with a porous sheet. Examples include, but are not limited to, porous sheet products.
  • the amorphous carbon-containing sheet according to one aspect of the present invention is not limited to sanitary products or medical products, and is used for various purposes in which it is desirable to exhibit high antibacterial or antiviral properties, such as curtains; automobile interior members; Rug such as rugs, carpets, mats; cloth products such as cushions, stuffed animals, bags (products in which cloth is used at least in part), and some or all of the cloth in the cloth products are replaced with porous sheets. It is also suitably used for porous sheet products.
  • the amorphous carbon-containing sheet product according to one aspect of the present invention is excellent in antibacterial and antiviral properties. Therefore, the amorphous carbon-containing sheet product according to one aspect of the present invention is suitable for applications in which these functions are effective.
  • Amorphous carbon-containing sheet products for antibacterial use and amorphous carbon-containing sheet products for antiviral use are also aspects of the present invention.
  • a method of imparting antibacterial or antiviral properties to a breathable sheet by adhering amorphous carbon to at least a part of the breathable sheet according to the above-mentioned method for producing an amorphous carbon-containing sheet is also available. This is one aspect of the present invention.
  • Example 1 Using a parallel plate type RF plasma CVD apparatus, a cotton cloth (JIS-L-0803 compliant test attachment white cloth Kanakin No. 3) was set in a base material holder in a vacuum chamber. After evacuating the inside of the vacuum chamber, hydrogen gas was introduced into the vacuum chamber so that the pressure in the vacuum chamber became 13.3 Pa, and 450 W RF (high frequency) power was supplied to the base material holder for 10 minutes. As a result, hydrogen plasma was generated to perform surface treatment (pretreatment) on the cotton cloth, and the surface (surface to be treated) was cleaned.
  • a cotton cloth JIS-L-0803 compliant test attachment white cloth Kanakin No. 3
  • 450 W RF high frequency
  • 500 W RF power was supplied to the base material holder for 90 minutes.
  • the temperature of the cotton cloth was maintained at 50 to 60 ° C. by cooling the cotton cloth with a water cooling mechanism in the base material holder.
  • amorphous carbon containing fluorine was attached to the surface (upper surface) of the cotton cloth.
  • the cotton cloth taken out from the vacuum chamber is set upside down again in the base material holder in the vacuum chamber, and the same operation as the above operation is repeated, and the surface (lower surface) of the cotton cloth contains fluorine.
  • Amorphous carbon-containing cloth was produced by adhering amorphous carbon to the upper and lower surfaces. The obtained amorphous carbon-containing cloth substantially retains the flexibility of the above-mentioned cotton cloth.
  • the fluorine content in the amorphous carbon was 17 at%.
  • Example 2 In the same manner as in Example 1, a surface treatment of a cotton cloth (JIS-L-0803 compliant test attachment white cloth Kanakin No. 3) was performed to clean the surface.
  • methane gas was introduced into the vacuum chamber as a plasma raw material gas so that the pressure in the vacuum chamber became 13.3 Pa, and 450 W RF power was supplied to the base material holder for 90 minutes.
  • the temperature of the cotton cloth was maintained at 50 to 60 ° C. by cooling the cotton cloth with a water cooling mechanism in the base material holder.
  • amorphous carbon was adhered to the surface (upper surface) of the cotton cloth.
  • the cotton cloth taken out from the vacuum chamber is set upside down again in the base material holder in the vacuum chamber, and the same operation as the above operation is repeated to obtain amorphous carbon on the surface (lower surface) of the cotton cloth.
  • amorphous carbon-containing cloth in which amorphous carbon was adhered to the upper and lower surfaces.
  • the obtained amorphous carbon-containing cloth substantially retains the flexibility of the above-mentioned cotton cloth.
  • the amorphous carbon-containing cloths obtained in Examples 1 and 2 are subjected to high-pressure steam sterilization treatment, and the same applies to the amorphous carbon-containing cloth after the high-pressure steam sterilization treatment.
  • the antibacterial activity was evaluated. High-pressure steam sterilization was repeated to see if the amorphous carbon-containing fabric could maintain a good antibacterial effect for a long period of time.
  • the high-pressure steam sterilization treatment was performed by adopting the sterilization treatment conditions (autoclave sterilization, steam temperature 126 ° C., sterilization time 15 minutes) used in the medical field.
  • the sterilization treatment conditions autoclave sterilization, steam temperature 126 ° C., sterilization time 15 minutes
  • a cotton cloth JIS-L-0803 compliant test attachment white cloth Kanakin No. 3 was used.
  • the antibacterial effect was evaluated by obtaining the antibacterial activity value of the test sample (and control sample) by the following test procedure.
  • each bacterial solution was added dropwise to a test sample (or control sample) in a vial, inoculated, and then cultured at 37 ° C. for 18 hours.
  • Mf represents the antibacterial activity value
  • Fa0 represents the viable cell count immediately after inoculation of the control sample
  • Fa1 represents the viable cell count after culturing the control sample
  • Fb0 represents the viable cell count.
  • the viable cell count immediately after inoculation of the test sample is represented
  • Fb1 represents the viable cell count after culturing the test sample.
  • the test sample is evaluated to have antibacterial properties.
  • the results are shown in FIGS. 1 to 4.
  • FIG. 1 is a graph showing the evaluation results of the antibacterial activity values of the amorphous carbon-containing cotton cloths of Examples 1 and 2 against Escherichia coli.
  • the amorphous carbon-containing cloths of both Example 1 and Example 2 have high antibacterial properties exceeding the measurement upper limit of 6.6.
  • the activity value was shown.
  • the amorphous carbon-containing cloth of Example 1 shows an antibacterial activity value exceeding the upper limit of measurement even after being subjected to the sterilization treatment 20 times, and has a high antibacterial activity exceeding 5 even after being subjected to the sterilization treatment 50 times. The value was maintained.
  • the amorphous carbon-containing cloth of Example 2 exhibited an antibacterial activity value exceeding 2 even after being sterilized 20 times, and maintained the antibacterial activity.
  • FIG. 2 is a graph showing the evaluation results of the antibacterial activity value of the amorphous carbon-containing cotton cloth of Example 1 and Example 2 against Staphylococcus aureus.
  • both the amorphous carbon-containing cloths of Example 1 and Example 2 showed a high antibacterial activity value exceeding the measurement upper limit of 4.7.
  • the amorphous carbon-containing cloth of Example 1 shows an antibacterial activity value exceeding the upper limit of measurement even after being sterilized 20 times, and has a high antibacterial activity exceeding 4 even after being sterilized 50 times. The value was maintained.
  • the amorphous carbon-containing cloth of Example 2 exhibited an antibacterial activity value exceeding 2 even after being sterilized 20 times, and maintained antibacterial properties.
  • FIG. 3 is a graph showing the evaluation results of the antibacterial activity value of the amorphous carbon-containing cotton cloth of Example 1 against Salmonella.
  • the amorphous carbon-containing cloth of Example 1 showed a high antibacterial activity value exceeding the measurement upper limit of 5.8.
  • the amorphous carbon-containing cloth of Example 1 maintained an antibacterial activity value exceeding the upper limit of measurement even after being sterilized 50 times.
  • FIG. 4 is a graph showing the evaluation results of the antibacterial activity value of the amorphous carbon-containing cotton cloth of Example 1 against Klebsiella pneumoniae.
  • the amorphous carbon-containing cloth of Example 1 showed a high antibacterial activity value exceeding the measurement upper limit of 5.8.
  • the amorphous carbon-containing cloth of Example 1 maintained an antibacterial activity value exceeding the upper limit of measurement even after being sterilized 20 times.
  • Example 1 The amorphous carbon-containing cloths obtained in Example 1 and Example 2 were evaluated for their antiviral property against influenza A virus (H3N2) according to the antiviral test method of JIS-L-1922: 2016.
  • the antiviral effect was evaluated by obtaining the antiviral activity value Mv of the test sample (and control sample) by the following test procedure.
  • a control sample a standard cloth specified in JIS-L-1922: 2016 was used.
  • the virus suspension was inoculated by dropping into a test sample (or control sample) in a vial, and then left at 25 ° C. for 2 hours.
  • Mv represents the antiviral activity value
  • Va represents the virus infectious titer immediately after inoculation of the control sample
  • Vb represents the virus infectious titer after leaving the test sample for 2 hours.
  • FIG. 5 is a graph showing the evaluation results of the antiviral property of the amorphous carbon-containing cloths of Examples 1 and 2 against influenza A virus (H3N2). Both the amorphous carbon-containing cloths of Example 1 and Example 2 showed a high antiviral activity value of more than 3.0, which was evaluated as having sufficient antiviral properties (Full effect). Furthermore, the amorphous carbon-containing cloth of Example 1 showed an antiviral activity value exceeding the measurement upper limit (4.3).
  • FIG. 6 is an SEM image showing the surfaces of the cotton cloth and the amorphous carbon-containing cloths of Examples 1 and 2 at a magnification of 100 times (upper row) and a magnification of 500 times (lower row).
  • FIG. 7 is an SEM image showing the surface of the cotton cloth at a magnification of 1000 times.
  • FIG. 8 is an SEM image showing the surface of the amorphous carbon-containing cloth of Example 1 at a magnification of 1000 times.
  • FIG. 9 is an SEM image showing the surface of the amorphous carbon-containing cloth of Example 2 at a magnification of 1000 times.
  • FIG. 10 is a photomicrograph of the surfaces of the cotton cloth and the amorphous carbon-containing cloths of Examples 1 and 2 observed with a microscope.
  • the photograph of FIG. 10 shows that the cotton cloth is white, whereas the amorphous carbon-containing cloths of Examples 1 and 2 are uniformly colored from yellow to light brown. Further, the photograph of FIG. 6 shows that the amorphous carbon-containing cloths of Examples 1 and 2 have a porous structure (mesh structure) by weaving fibers, which is substantially the same as that of the cotton cloth. .. Further, the photographs of FIGS. 7 to 9 show that in the amorphous carbon-containing cloths of Examples 1 and 2, the amorphous carbon is formed so as to cover the surface of the fibers of the cotton cloth. According to FIGS. 7 to 9, in the amorphous carbon-containing cloth of the example, the fibers are substantially independent of each other even if the surface is covered with amorphous carbon, and the fibers are substantially independent of each other. It can be seen that it is not bound to.
  • the amorphous carbon is used on the surface of the fibers without binding the fibers constituting the cloth. It was confirmed that it adhered so as to cover at least a part.
  • amorphous carbon-containing cloths of Examples 1 and 2 show antiviral properties. That is, since the fibers of the cotton cloth form a porous structure and the surface of the porous structure is covered with amorphous carbon, until the virus adheres to the surface of the amorphous carbon-containing cloth, or It is thought that this is because the virus is inactivated as a result of contact with amorphous carbon at a high frequency when it floats again after attachment.
  • the present invention can be particularly suitably used for sanitary products or medical products.

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Abstract

L'invention concerne une feuille contenant du carbone non cristallin ayant une propriété antimicrobienne ou une propriété antivirale. La feuille contenant du carbone non cristallin est obtenue par liaison de carbone non cristallin sur au moins une partie d'une feuille perméable aux gaz. Il est ainsi possible de fournir une feuille contenant du carbone non cristallin ayant une propriété antimicrobienne ou une propriété antivirale.
PCT/JP2020/034661 2019-10-11 2020-09-14 Feuille contenant du carbone non cristallin, produit en feuille contenant du carbone non cristallin et procédé pour conférer une propriété antimicrobienne ou une propriété anti-virale à une feuille perméable aux gaz WO2021070566A1 (fr)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005536635A (ja) * 2002-08-26 2005-12-02 シグマ・ラボラトリーズ・オブ・アリゾナ・インコーポレーテツド 大気圧グロー放電により生成された遮断被膜
JP2015081370A (ja) * 2013-10-23 2015-04-27 トーカロ株式会社 抗菌性ｄｌｃ膜被覆部材およびその製造方法
WO2016056466A1 (fr) * 2014-10-05 2016-04-14 太陽誘電ケミカルテクノロジー株式会社 Structure de stratifié antibactérien et procédé pour sa fabrication
JP2018199319A (ja) * 2017-05-29 2018-12-20 株式会社都ローラー工業 Ｃｄ又は／及びｄｌｃ固着基材とそれら基材を使用した製品
WO2019045110A1 (fr) * 2017-09-04 2019-03-07 株式会社Ｎｂｃメッシュテック Composition antibactérienne/antivirale
JP2020033592A (ja) * 2018-08-29 2020-03-05 学校法人東京電機大学 非晶質炭素膜とその製造方法

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018088459A1 (fr) * 2016-11-11 2018-05-17 学校法人金沢医科大学 Élément antibactérien

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005536635A (ja) * 2002-08-26 2005-12-02 シグマ・ラボラトリーズ・オブ・アリゾナ・インコーポレーテツド 大気圧グロー放電により生成された遮断被膜
JP2015081370A (ja) * 2013-10-23 2015-04-27 トーカロ株式会社 抗菌性ｄｌｃ膜被覆部材およびその製造方法
WO2016056466A1 (fr) * 2014-10-05 2016-04-14 太陽誘電ケミカルテクノロジー株式会社 Structure de stratifié antibactérien et procédé pour sa fabrication
JP2018199319A (ja) * 2017-05-29 2018-12-20 株式会社都ローラー工業 Ｃｄ又は／及びｄｌｃ固着基材とそれら基材を使用した製品
WO2019045110A1 (fr) * 2017-09-04 2019-03-07 株式会社Ｎｂｃメッシュテック Composition antibactérienne/antivirale
JP2020033592A (ja) * 2018-08-29 2020-03-05 学校法人東京電機大学 非晶質炭素膜とその製造方法

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