EP3945154A1 - Matière fibreuse à revêtement de manganoxyde - Google Patents

Matière fibreuse à revêtement de manganoxyde Download PDF

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Publication number
EP3945154A1
EP3945154A1 EP20188829.4A EP20188829A EP3945154A1 EP 3945154 A1 EP3945154 A1 EP 3945154A1 EP 20188829 A EP20188829 A EP 20188829A EP 3945154 A1 EP3945154 A1 EP 3945154A1
Authority
EP
European Patent Office
Prior art keywords
manganese
oxide
manganese oxide
fiber material
fibrous material
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP20188829.4A
Other languages
German (de)
English (en)
Inventor
Jens Dahl Jensen
Ursus KRÜGER
Gabriele Winkler
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Siemens AG
Siemens Corp
Original Assignee
Siemens AG
Siemens Corp
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 Siemens AG, Siemens Corp filed Critical Siemens AG
Priority to EP20188829.4A priority Critical patent/EP3945154A1/fr
Priority to CN202180058468.4A priority patent/CN116194635B/zh
Priority to PCT/EP2021/069726 priority patent/WO2022023052A1/fr
Priority to US18/007,375 priority patent/US20230295868A1/en
Priority to EP21746410.6A priority patent/EP4143377A1/fr
Publication of EP3945154A1 publication Critical patent/EP3945154A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • D06M11/48—Oxides or hydroxides of chromium, molybdenum or tungsten; Chromates; Dichromates; Molybdates; Tungstates
    • D06M11/485—Oxides or hydroxides of manganese; Manganates
    • 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
    • A41D13/1192—Protective face masks, e.g. for surgical use, or for use in foul atmospheres with antimicrobial agent
    • A—HUMAN NECESSITIES
    • A41—WEARING APPAREL
    • A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
    • A41D31/00—Materials specially adapted for outerwear
    • A41D31/04—Materials specially adapted for outerwear characterised by special function or use
    • A41D31/30—Antimicrobial, e.g. antibacterial
    • 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
    • D06M10/00—Physical treatment of fibres, threads, yarns, fabrics or fibrous goods made from such materials, e.g. by ultrasonic waves, corona discharge, irradiation, electric currents or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
    • D06M10/02—Sonic or ultrasonic waves; Corona discharge
    • D06M10/025—Corona discharge or low temperature plasma
    • 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
    • D06M10/00—Physical treatment of fibres, threads, yarns, fabrics or fibrous goods made from such materials, e.g. by ultrasonic waves, corona discharge, irradiation, electric currents or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
    • D06M10/04—Physical treatment combined with treatment with chemical compounds or elements
    • D06M10/06—Inorganic compounds or elements
    • 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
    • D06M11/83—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 metals; with metal-generating compounds, e.g. metal carbonyls; Reduction of metal compounds on textiles
    • 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
    • D06M16/00—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic
    • 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

Definitions

  • the invention relates to a method for coating a fiber material, in particular a fleece, with manganese oxide, a method for producing an antiviral and antibacterial layer and a fiber material with manganese oxide.
  • Fibrous materials in particular fleece materials, which consist of plastics such as polypropylene or polyamide fibers or also of cellulose-based materials, are provided with an antibacterial or antiviral layer for use in respirator masks.
  • fleece materials which consist of plastics such as polypropylene or polyamide fibers or also of cellulose-based materials
  • an antibacterial or antiviral layer for use in respirator masks.
  • the proportion of manganese (IV) oxide can be increased to 80% by an annealing process at over 400°C in the presence of oxygen. These high temperatures are particularly Synthetic fiber materials, eg non-woven materials, are not possible as they would be thermally damaged or even decomposed.
  • the invention is based on the object of specifying a method which makes it possible to increase the proportion of manganese(IV) oxide without damaging the fiber material. Furthermore, the object of the invention is to specify a fiber material with an increased proportion of manganese(IV) oxide.
  • the manganese oxide precipitate usually comprises manganese oxides in different oxidation states, which are oxidized with the present method to a high quality manganese (IV) oxide layer.
  • the annealing process known from the prior art at 400° C. or above is replaced by another energy-transferring process.
  • the manganese oxide precipitate is applied wet-chemically, in particular from potassium permanganate and manganese(II) salts.
  • the manganese oxide precipitate can, for example, be sprayed onto the fiber material via nozzles as a potassium permanganate solution and as a manganese(II) salt solution (possible salts here are, for example, nitrate or acetate).
  • a mixture of manganese oxides of different oxidation states precipitates.
  • the precipitate is preferably dried by a heating system, in particular to remove water. 110°C has proven to be advantageous here.
  • the manganese oxide precipitate is oxidized by an oxygen plasma.
  • Oxidation by means of oxygen plasma has the advantage that, at relatively low temperatures, in particular below 200° C., a high oxidation rate of the various manganese oxides to form manganese(IV) oxide is possible. This further improves the properties of the fiber material.
  • the fiber material can be placed in a vacuum system and treated with oxygen plasma, e.g . B. be treated via a hollow cathode plasma source.
  • the method includes removing hydroxyl groups from the manganese(IV) oxide layer.
  • the removal of the hydroxyl groups can be carried out particularly advantageously in one step with the oxidation under oxygen plasma.
  • the negative oxygen ions react with the manganese(II) oxide and the manganese(III) oxide to form the bactericidal manganese(IV) oxide and at the same time the hydroxyl groups and water molecules adhering to the manganese oxide mixture are released as water vapor via a Removed turbopump on a vacuum chamber.
  • the method comprises applying silver to the fiber material which has been provided with manganese(IV) oxide according to the method according to the invention. This step is advantageously carried out after the manganese (IV) oxide has been applied. This forms an antibacterial and antiviral layer with a very good effect.
  • the silver is applied as a silver nitrate solution and reduced to silver by means of a reducing agent. This can be done with jet-coated silver nitrate solution and hypophosphorous acid as a reducing agent for the silver nitrate.
  • the fiber material is dried under a protective gas atmosphere.
  • the fleece is dried under a protective gas atmosphere (nitrogen or argon).
  • a protective gas atmosphere nitrogen or argon
  • 110°C has proven advantageous for drying, also to remove residual water.
  • the protective gas atmosphere is advantageous so that the silver does not oxidize.
  • the order in which the bactericidal active substances are deposited is also advantageous in this process, since the manganese(IV) oxide is applied first and then the silver because of the risk of oxidation of the silver. This results in improved chemical contact between the silver and the manganese oxide.
  • the object is also achieved by a fiber material which has a manganese oxide coating which has at least 70% by weight of manganese(IV) oxide based on the manganese oxide coating.
  • the weight in % based on the manganese oxide coating is determined without the weight of the fibers. At least 75% by weight of the manganese oxide coating is advantageous. With the method according to the invention, 80% by weight or more by weight with respect to the manganese oxide coating is also possible.
  • the fiber material has a particularly high concentration of manganese(IV) oxide.
  • the manganese oxide coating has less than 5% by weight, in particular less than 1% by weight, of manganese(II) oxide, based on the total weight of the manganese oxide coating.
  • the fiber material has a melting temperature below 200°C. Fibers with a melting temperature of below 180°C or even 160°C can also be advantageously selected. This expands the choice of materials, especially for skin-friendly fleece materials, e.g. B. Polypropylene.
  • the fiber material contains silver. In order to achieve an improved antibacterial and antiviral effect, the fiber material contains silver.
  • the fiber material can also have plastic fibers, in particular polypropylene fibers.
  • the fiber material can consist entirely of the plastic fibers that are coated with the manganese oxide layer.
  • a mouth and nose protector comprising a fiber material according to the invention.
  • the fiber material can also be used in personal protective equipment.
  • FIG 1 shows a system 100 that can process fiber material 10 and provide it with a manganese oxide coating.
  • fiber material 10 z.
  • B Nonwovens made of plastics that are used in respirators, such as polypropylene or polyamide fibers in question.
  • the system 100 has a first roller 101 on which the fiber material 10 is delivered and which makes the fiber material 10 available for transport through the system 100 .
  • the system also has a second roll 102 onto which the finished fiber material is rolled up.
  • the rollers 101, 102 can be designed as transportable transport rollers.
  • the system 100 also has a first nozzle 121 that applies the potassium permanganate solution and a second nozzle 122 that applies the manganese(II) salt solution or manganese(II) acetate solution to the fiber material 10 .
  • a fleece made of plastic can thus be sprayed through the nozzles 121, 122 with a potassium permanganate solution and a manganese(II) salt solution, nitrate or acetate being usable as the salt.
  • a first heating system 130 dries the resulting manganese oxide precipitate, in particular at 110°C.
  • Fibrous materials 10 made of plastic usually withstand temperatures of up to a maximum of 160° C., in special cases up to 200° C., then these plastics melt and decomposition takes place at even higher temperatures. Therefore, in plant 100, a possible annealing process at 400°C was replaced by another energy-transferring process.
  • the system 100 has a plasma generator 110, which offers the possibility of applying oxygen plasma 112 to the fiber material 10 provided with the dried manganese oxide precipitate.
  • a plasma process e.g. hollow cathode plasma, inductively coupled plasma, capacitively coupled plasma or Microwave plasma
  • oxygen molecules and oxygen atoms can be ionized. This creates atomic oxygen and oxygen ions O - , O 2 - , O 3 - , which with react with the manganese oxide surface produced shortly beforehand in the plant and this oxidizes into the corresponding manganese (IV) oxide.
  • a hollow cathode plasma source as the plasma generator 110 is preferred because the hollow cathode, due to its shape, can trap oxygen ions and electrons in its cavities, thus providing a higher plasma (electron) density. Also, after plasma ignition, the voltage drops, but a further increase in current does not produce a larger increase in voltage. In contrast, with capacitively or inductively coupled plasma sources, the voltage increases continuously with the current. This high voltage potential is accelerated by the ions, which receive such a high excess of energy that the substrate surface can be damaged. With the hollow cathode, the plasma potential remains low so that the ions absorb less energy and do not damage the substrate surface.
  • the fiber material 10, e.g. B. a plastic fleece can be introduced into a vacuum chamber.
  • oxygen is introduced into a hollow cathode plasma source.
  • this plasma generator 110 which is designed as a hollow cathode plasma source, high voltage (100 to 300 volts) is generated between the anode and cathode via a radio-frequency plasma generator and impedance differences (AC resistances) that occur are minimized and adjusted in a matching box.
  • the oxygen molecules can be ionized at 12.06 eV and the oxygen atom at 13.62 eV.
  • the discharge of the oxygen molecules occurs mainly through direct electron impact dissociation and through dissociative electron attachment. Unstable, excited O 2 - * are formed as intermediate products, which then decompose into atomic oxygen and oxygen ions. Oxygen discharges are weakly negative, this means that a fraction of the negative charge is made up of ions instead of electrons.
  • the negative ions are O- , O 2 and even O 3- . These negative oxygen ions react with the manganese (II) oxide and the manganese (III) oxide to form the bactericidal manganese (IV) oxide and at the same time the hydroxyl groups and water molecules adhering to the manganese oxide mixture are removed as water vapor. This can be done by a turbo pump 114 on a vacuum chamber.
  • Nonwovens mainly consisting of plastics and cellulose-based materials, can be easily coated in a roll-to-roll process.
  • a silver nitrate solution is then sprayed through a third nozzle 123 and a reducing agent for the silver nitrate (e.g. hypophosphorous acid) through a fourth nozzle 124 onto the fiber material 10 coated/adhered to with manganese(IV) oxide.
  • a reducing agent for the silver nitrate e.g. hypophosphorous acid
  • the fiber material 10 is dried in a second heating system 140, preferably under a protective gas atmosphere (nitrogen or argon) at preferably 110°C. Drying removes excess water.
  • the protective gas atmosphere is advantageous so that the silver does not oxidize.
  • the order in which the bactericidal active substances are deposited is also advantageous in this process.
  • the fleece can be moved automatically via the transport rollers 101, 102.
  • the system 100 can be controlled with the aid of a computer via an electronic controller.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Plasma & Fusion (AREA)
  • Biochemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Microbiology (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Physical Education & Sports Medicine (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
  • Catalysts (AREA)
EP20188829.4A 2020-07-31 2020-07-31 Matière fibreuse à revêtement de manganoxyde Withdrawn EP3945154A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
EP20188829.4A EP3945154A1 (fr) 2020-07-31 2020-07-31 Matière fibreuse à revêtement de manganoxyde
CN202180058468.4A CN116194635B (zh) 2020-07-31 2021-07-15 具有锰氧化物涂层的纤维材料
PCT/EP2021/069726 WO2022023052A1 (fr) 2020-07-31 2021-07-15 Matériau fibreux ayant un revêtement d'oxyde de manganèse
US18/007,375 US20230295868A1 (en) 2020-07-31 2021-07-15 Fiber Material Having a Manganese Oxide Coating
EP21746410.6A EP4143377A1 (fr) 2020-07-31 2021-07-15 Matériau fibreux ayant un revêtement d'oxyde de manganèse

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP20188829.4A EP3945154A1 (fr) 2020-07-31 2020-07-31 Matière fibreuse à revêtement de manganoxyde

Publications (1)

Publication Number Publication Date
EP3945154A1 true EP3945154A1 (fr) 2022-02-02

Family

ID=71899534

Family Applications (2)

Application Number Title Priority Date Filing Date
EP20188829.4A Withdrawn EP3945154A1 (fr) 2020-07-31 2020-07-31 Matière fibreuse à revêtement de manganoxyde
EP21746410.6A Pending EP4143377A1 (fr) 2020-07-31 2021-07-15 Matériau fibreux ayant un revêtement d'oxyde de manganèse

Family Applications After (1)

Application Number Title Priority Date Filing Date
EP21746410.6A Pending EP4143377A1 (fr) 2020-07-31 2021-07-15 Matériau fibreux ayant un revêtement d'oxyde de manganèse

Country Status (4)

Country Link
US (1) US20230295868A1 (fr)
EP (2) EP3945154A1 (fr)
CN (1) CN116194635B (fr)
WO (1) WO2022023052A1 (fr)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105249567A (zh) * 2015-11-18 2016-01-20 华文蔚 一种一次性无纺布口罩
CN105725310A (zh) * 2016-05-03 2016-07-06 韩淑敏 具有增氧功能的口罩
CN107455822A (zh) * 2017-09-12 2017-12-12 江苏纳纤新材料科技有限公司 一种纳米纤维‑微米纤维复合防雾霾口罩
KR102108768B1 (ko) * 2019-06-18 2020-05-08 홍창석 항균 마스크.

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6517974B1 (en) * 1998-01-30 2003-02-11 Canon Kabushiki Kaisha Lithium secondary battery and method of manufacturing the lithium secondary battery
FR2857030B1 (fr) * 2003-07-01 2006-10-27 Saint Gobain Procede de depot d'oxyde de titane par source plasma
JP5320710B2 (ja) * 2007-09-07 2013-10-23 ソニー株式会社 正極活物質及びその製造方法、並びに電気化学デバイス
WO2012167280A1 (fr) * 2011-06-03 2012-12-06 The Regents Of The University Of California Oxyde de manganèse et fibres de charbon actif permettant d'éliminer une particule, un cov ou de l'ozone contenu(e) dans un gaz
KR102805431B1 (ko) * 2015-10-08 2025-05-12 알심 에너지, 인크. 재충전가능 알루미늄 이온 배터리
CN108642887A (zh) * 2018-04-20 2018-10-12 宿迁南航新材料与装备制造研究院有限公司 一种可穿戴保健材料

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105249567A (zh) * 2015-11-18 2016-01-20 华文蔚 一种一次性无纺布口罩
CN105725310A (zh) * 2016-05-03 2016-07-06 韩淑敏 具有增氧功能的口罩
CN107455822A (zh) * 2017-09-12 2017-12-12 江苏纳纤新材料科技有限公司 一种纳米纤维‑微米纤维复合防雾霾口罩
KR102108768B1 (ko) * 2019-06-18 2020-05-08 홍창석 항균 마스크.

Also Published As

Publication number Publication date
US20230295868A1 (en) 2023-09-21
CN116194635B (zh) 2025-05-09
CN116194635A (zh) 2023-05-30
WO2022023052A1 (fr) 2022-02-03
EP4143377A1 (fr) 2023-03-08

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