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CN111802405B - Aqueous solution antibacterial disinfectant and preparation method and application thereof - Google Patents

Aqueous solution antibacterial disinfectant and preparation method and application thereof Download PDF

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Publication number
CN111802405B
CN111802405B CN202010844415.2A CN202010844415A CN111802405B CN 111802405 B CN111802405 B CN 111802405B CN 202010844415 A CN202010844415 A CN 202010844415A CN 111802405 B CN111802405 B CN 111802405B
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aqueous
disinfectant
oxide
antibacterial
antibacterial disinfectant
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CN111802405A (en
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林玉平
程斌
孙卓然
林雪
李杨
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Sanhe Anba Biotechnology Co ltd
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Sanhe Anba Biotechnology Co ltd
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    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N59/00Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • A01N59/16Heavy metals; Compounds thereof
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/02Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N59/00Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N59/00Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • A01N59/06Aluminium; Calcium; Magnesium; Compounds thereof
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K33/00Medicinal preparations containing inorganic active ingredients
    • A61K33/24Heavy metals; Compounds thereof
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K9/00Medicinal preparations characterised by special physical form
    • A61K9/0012Galenical forms characterised by the site of application
    • A61K9/0014Skin, i.e. galenical aspects of topical compositions
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K9/00Medicinal preparations characterised by special physical form
    • A61K9/06Ointments; Bases therefor; Other semi-solid forms, e.g. creams, sticks, gels
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K9/00Medicinal preparations characterised by special physical form
    • A61K9/08Solutions
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L26/00Chemical aspects of, or use of materials for, wound dressings or bandages in liquid, gel or powder form
    • A61L26/0004Chemical aspects of, or use of materials for, wound dressings or bandages in liquid, gel or powder form containing inorganic materials
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L26/00Chemical aspects of, or use of materials for, wound dressings or bandages in liquid, gel or powder form
    • A61L26/0061Use of materials characterised by their function or physical properties
    • A61L26/0066Medicaments; Biocides
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61PSPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P1/00Drugs for disorders of the alimentary tract or the digestive system
    • A61P1/02Stomatological preparations, e.g. drugs for caries, aphtae, periodontitis
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61PSPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P17/00Drugs for dermatological disorders
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61PSPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P31/00Antiinfectives, i.e. antibiotics, antiseptics, chemotherapeutics
    • A61P31/02Local antiseptics
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61PSPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P31/00Antiinfectives, i.e. antibiotics, antiseptics, chemotherapeutics
    • A61P31/04Antibacterial agents
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61PSPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P31/00Antiinfectives, i.e. antibiotics, antiseptics, chemotherapeutics
    • A61P31/10Antimycotics
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61PSPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P31/00Antiinfectives, i.e. antibiotics, antiseptics, chemotherapeutics
    • A61P31/12Antivirals
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q11/00Preparations for care of the teeth, of the oral cavity or of dentures; Dentifrices, e.g. toothpastes; Mouth rinses
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00Nanotechnology for materials or surface science, e.g. nanocomposites
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00Manufacture or treatment of nanostructures
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/14Paints containing biocides, e.g. fungicides, insecticides or pesticides
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00Treating 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
    • D06M11/32Treating 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
    • D06M11/36Treating 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
    • D06M11/45Oxides or hydroxides of elements of Groups 3 or 13 of the Periodic Table; Aluminates
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00Treating 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
    • D06M11/32Treating 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
    • D06M11/36Treating 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
    • D06M11/46Oxides or hydroxides of elements of Groups 4 or 14 of the Periodic Table; Titanates; Zirconates; Stannates; Plumbates
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00Treating 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
    • D06M11/32Treating 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
    • D06M11/36Treating 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
    • D06M11/48Oxides or hydroxides of chromium, molybdenum or tungsten; Chromates; Dichromates; Molybdates; Tungstates
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    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00Treating 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
    • D06M11/77Treating 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 silicon or compounds thereof
    • D06M11/79Treating 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 silicon or compounds thereof with silicon dioxide, silicic acids or their salts
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M16/00Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L2300/00Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/10Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing inorganic materials
    • A61L2300/102Metals or metal compounds, e.g. salts such as bicarbonates, carbonates, oxides, zeolites, silicates
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    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
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    • A61L2300/00Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/40Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a specific therapeutic activity or mode of action
    • A61L2300/404Biocides, antimicrobial agents, antiseptic agents
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    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
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    • A61L2300/00Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/40Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a specific therapeutic activity or mode of action
    • A61L2300/404Biocides, antimicrobial agents, antiseptic agents
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Abstract

The application discloses an aqueous solution antibacterial disinfectant, which contains molybdenum element and other elements, wherein the content of the molybdenum element in the aqueous solution antibacterial disinfectant is 0.1-0.9 wt%, and the content of the other elements is 0-0.5 wt%; the application also provides a preparation method of the aqueous solution antibacterial disinfectant. The application provides an aqueous solution antibacterial disinfectant, which has strong sterilization and disinfection functions, can be used for an antibacterial coating formed by water-based paint, and can also be applied to objects such as metal, fabric, ceramic and the like to enable the surface of the objects to have antibacterial performance.

Description

Aqueous solution antibacterial disinfectant and preparation method and application thereof
Technical Field
The application relates to the technical field of antibacterial agents, in particular to an aqueous solution antibacterial disinfectant and a preparation method and application thereof.
Background
The bacteria are microorganisms associated with human beings, and pathogenic bacteria can cause diseases to human beings, lose working capacity and even die. Human development history is also a history of fighting against bacteria. For example: silver and copper are highly effective antibacterial agents discovered by people and used up to now. In the last fifty years, with the development of science and technology, high-efficiency antibacterial agents are continuously developed.
At present, the commonly used high-efficiency antibacterial agents comprise silver, titanium oxide, zinc oxide, quaternary ammonium salt and the like, and are widely applied. However, silver and the like have high cost and are greatly influenced by the environment, and titanium dioxide and the like rely on ultraviolet light and have no bactericidal property under the condition of no light; organic matters such as quaternary ammonium salt and the like are easy to degrade and have poor durability.
Disclosure of Invention
In view of the above, the present application provides an aqueous antibacterial disinfectant, which has strong sterilization and disinfection functions, and can be applied to objects such as metal, fabric, ceramic, etc. to make the surfaces of the objects have antibacterial properties.
In order to accomplish the above objects, according to one aspect of the present application, there is provided an aqueous antibacterial disinfectant and a method for preparing the same.
The present application provides the following technical solutions.
1. An aqueous solution antibacterial disinfectant is characterized by comprising 0.1-0.9 wt% of molybdenum element and preferably 0.3-0.5 wt% of other elements, and 0-0.2 wt% of the aqueous solution antibacterial disinfectant and preferably 0.005-0.02 wt% of the other elements.
2. An aqueous antimicrobial disinfectant according to item 1, wherein said aqueous antimicrobial disinfectant is formed from water and molybdenum oxide.
3. An aqueous antibacterial disinfectant according to item 1, wherein said aqueous antibacterial disinfectant is formed of water, molybdenum oxide and oxides of other elements.
4. An aqueous antibacterial disinfectant according to item 1, wherein said other element is selected from one or more of silicon, aluminum and titanium, and said other element is preferably silicon.
5. An aqueous antibacterial disinfectant according to claim 3, wherein the oxide of other element is one or more of silicon oxide, aluminum oxide and titanium oxide, preferably silicon oxide, more preferably nano-scale silicon oxide;
the purity of the nano-grade silicon oxide is 99-99.9%, preferably 99.8%, the average particle diameter is 5-90nm, preferably 30nm, the specific surface area is 100-300m2A/g of preferably 200. + -.25 m2/g。
6. An aqueous antibacterial disinfectant according to item 3, wherein the mass ratio of the molybdenum oxide to the other oxides is 1: (0-35) but excluding 0, preferably 1 (4-6).
7. An aqueous antibacterial disinfectant according to item 1, wherein the pH of the aqueous antibacterial disinfectant is 1.5 to 3.5, preferably 1.6 to 2.5.
8. An aqueous antibacterial disinfectant according to item 1, wherein the content of molybdenum and/or other elements in the aqueous antibacterial disinfectant is detected by using an X-ray fluorescence spectrometer.
9. A preparation method of an aqueous solution antibacterial disinfectant is characterized by comprising the following steps:
adding molybdenum oxide and/or oxides of other elements into water, heating and stirring to dissolve the molybdenum oxide and/or oxides of other elements to form a mixed solution;
subsequently cooling the mixture to cool the solution to room temperature;
and filtering the mixed solution cooled to room temperature to remove undissolved solid insoluble substances so as to obtain the aqueous solution antibacterial disinfectant.
10. The method of preparing an aqueous antibacterial disinfectant according to item 9, wherein the water is contained in an amount of 3 to 35 times, preferably 20 times, the amount of the oxide substance of molybdenum oxide and/or other elements.
11. The method for preparing an aqueous antibacterial disinfectant according to item 9, wherein the temperature for heating and dissolving is 50 ℃ to 130 ℃, preferably 90 ℃ to 110 ℃, and the temperature is maintained for 10min to 5h, preferably 2h to 5 h.
12. The method of claim 9, wherein the cooling is performed by natural cooling or other physical cooling to room temperature.
13. The method for preparing the aqueous solution antibacterial disinfectant, according to the item 9, characterized in that the filtration is performed by using 2500-12500 mesh polypropylene PP microfiltration membrane, preferably 12500 mesh polypropylene PP microfiltration membrane.
14. The method for preparing an aqueous antibacterial disinfectant according to claim 9, wherein the oxide of the other element is one or more of silicon oxide, aluminum oxide and titanium oxide, preferably silicon oxide, more preferably nano-scale silicon oxide;
the purity of the nano-grade silicon oxide is 99-99.9%, preferably 99.8%, the average particle diameter is 5-90nm, preferably 30nm, the specific surface area is 100-300m2A/g of preferably 200. + -.25 m2/g。
15. The method for preparing an aqueous antibacterial disinfectant according to item 9, wherein the content of molybdenum in the aqueous antibacterial disinfectant is 0.1wt% to 0.9wt%, preferably 0.3wt% to 0.5wt%, and the content of other elements is 0 to 0.2wt%, preferably 0.005wt% to 0.02 wt%.
16. The method of claim 9, wherein the mass ratio of the molybdenum oxide to the other oxides is 1: (0-35).
17. The method for preparing an aqueous antibacterial disinfectant according to item 16, wherein the mass ratio of the molybdenum oxide to the other oxides is 1: 0.
18. The method for preparing an aqueous antibacterial disinfectant according to item 16, wherein the mass ratio of the molybdenum oxide to the other oxides is 1 (4-6).
19. The method of preparing an aqueous antibacterial disinfectant according to item 18, wherein the pH of the aqueous antibacterial disinfectant is 1.5 to 3.5, preferably 1.6 to 2.5.
20. The method of preparing an aqueous antibacterial disinfectant according to item 17, wherein the pH of the aqueous antibacterial disinfectant is 2.2 to 2.6, preferably 2.5.
21. Use of an aqueous antimicrobial disinfectant according to any one of claims 1 to 8 or prepared by the method of any one of claims 9 to 20 in an antimicrobial coating formed from an aqueous coating or in the antimicrobial treatment of metal, textile, wood, ceramic, plastic surfaces.
22. An antibacterial disinfectant for application to surfaces of metal, fabric, wood, ceramic, and plastic, comprising the aqueous antibacterial disinfectant according to any one of items 1 to 8 or the aqueous antibacterial disinfectant prepared by the preparation method of any one of items 9 to 20.
The water solution antibacterial disinfectant provided by the application not only has antibacterial and disinfecting functions, but also is convenient to apply, can be conveniently applied to water-based paint or the surfaces of fabrics, wood, metal, ceramics and plastics, and still has the antibacterial function on the material surface after drying.
Detailed Description
The following description of the exemplary embodiments of the present application is provided in connection with the understanding that the various details of the embodiments of the present application are included to facilitate understanding and should be considered exemplary only. Accordingly, those of ordinary skill in the art will recognize that various changes and modifications of the embodiments described herein can be made without departing from the scope and spirit of the present application. Also, descriptions of well-known functions and constructions are omitted in the following description for clarity and conciseness.
The application provides an aqueous solution antibacterial disinfectant, which contains molybdenum element and other elements, wherein the content of the molybdenum element in the aqueous solution antibacterial disinfectant is 0.1wt% -0.9 wt%, preferably 0.3wt% -0.5 wt%, and the content of the other elements is 0-0.2 wt%, preferably 0.005wt% -0.02 wt%.
The content of molybdenum element in the aqueous antibacterial disinfectant may be 0.1wt%, 0.11 wt%, 0.12 wt%, 0.13 wt%, 0.14 wt%, 0.15 wt%, 0.16 wt%, 0.17 wt%, 0.18 wt%, 0.19 wt%, 0.2wt%, 0.21 wt%, 0.22 wt%, 0.23 wt%, 0.24 wt%, 0.25 wt%, 0.26 wt%, 0.27 wt%, 0.28 wt%, 0.29 wt%, 0.3wt%, 0.31 wt%, 0.32 wt%, 0.33 wt%, 0.34 wt%, 0.35 wt%, 0.36 wt%, 0.37 wt%, 0.38 wt%, 0.39 wt%, 0.4 wt%, 0.41 wt%, 0.42 wt%, 0.43 wt%, 0.44 wt%, 0.45 wt%, 0.46 wt%, 0.47 wt%, 0.48 wt%, 0.49 wt%, 0.5wt%, 0.51 wt%, 0.54 wt%, 0.53 wt%, 0.58 wt%, 0.54 wt%, 0.53 wt%, 0.55 wt%, 0.53 wt%, 0.58 wt%, 0.55 wt%, 0.60 wt%, 0.23 wt%, 0.60 wt%, 0., 0.68 wt%, 0.69 wt%, 0.7 wt%, 0.71 wt%, 0.72 wt%, 0.73 wt%, 0.74 wt%, 0.75 wt%, 0.76 wt%, 0.77 wt%, 0.78 wt%, 0.79 wt%, 0.8 wt%, 0.81 wt%, 0.82 wt%, 0.83 wt%, 0.84 wt%, 0.85 wt%, 0.86 wt%, 0.87 wt%, 0.88 wt%, 0.89 wt%, 0.9 wt%.
The content of the other element may be 0 wt%, 0.05 wt%, 0.06 wt%, 0.07 wt%, 0.08 wt%, 0.09 wt%, 0.1wt%, 0.11 wt%, 0.12 wt%, 0.13 wt%, 0.14 wt%, 0.15 wt%, 0.16 wt%, 0.17 wt%, 0.18 wt%, 0.19 wt%, 0.2 wt%.
The aqueous antimicrobial disinfectant may be formed from water, molybdenum oxide, and oxides of other elements.
The aqueous antimicrobial disinfectant may be formed from water, molybdenum oxide.
In the present application, the other element is selected from one or two or more of silicon, aluminum, and titanium, and preferably silicon.
In the present application, the other element may be silicon.
In the present application, the other element may be aluminum.
In the present application, the other element may be titanium.
In the present application, the other elements may be silicon and aluminum.
In the present application, the other elements may be silicon and titanium.
In the present application, the other elements may be aluminum and titanium.
In the present application, the other elements may be silicon, aluminum, and titanium.
In the present application, the oxide of the other element is one or two or more of silicon oxide, aluminum oxide, and titanium oxide, preferably silicon oxide, and more preferably nano-scale silicon oxide.
In the present application, the oxide of the other element may be nano-scale silicon oxide.
In the present application, the oxide of the other element may be alumina.
In the present application, the oxide of the other element may be titanium oxide.
In the present application, the oxides of the other elements may be nano-scale silicon oxide and aluminum oxide.
In the present application, the oxide of the other element may be nano-scale silicon oxide and titanium oxide.
In the present application, the oxide of the other element may be alumina and titania.
In the present application, the oxide of the other element may be alumina, nano-scale silica, and titania.
The purity of the nano-silicon oxide is 99-99.9%, preferably 99.8%, the average particle diameter is 5-90nm (the average particle diameter is the primary particle diameter of an electron microscope), preferably 30nm, the specific surface area is 100-300m2A/g of preferably 200. + -.25 m2/g。
The nano-scale silica may have an average particle diameter of 5nm, 6nm, 7nm, 8nm, 9nm, 10nm, 11nm, 12nm, 13nm, 14nm, 15nm, 16nm, 17nm, 18nm, 19nm, 20nm, 21nm, 22nm, 23nm, 24nm, 25nm, 26nm, 27nm, 28nm, 29nm, 30nm, 31nm, 32nm, 33nm, 34nm, 35nm, 36nm, 37nm, 38nm, 39nm, 40nm, 41nm, 42nm, 43nm, 44nm, 45nm, 46nm, 47nm, 48nm, 49nm, 50nm, 51nm, 52nm, 53nm, 54nm, 55nm, 56nm, 57nm, 58nm, 59nm, 60nm, 61nm, 62nm, 63nm, 64nm, 65nm, 66nm, 67nm, 68nm, 69nm, 70nm, 71nm, 72nm, 73nm, 76nm, 78nm, 79nm, 82nm, 79nm, 78nm, 82nm, 65nm, 71nm, 72nm, 73nm, 77nm, 82nm, or a, 83nm, 84nm, 85nm, 86nm, 87nm, 88nm, 89nm and 90 nm.
In the present application, when the aqueous antibacterial disinfectant may be formed of water, molybdenum oxide, and oxides of other elements, the mass ratio of the molybdenum oxide to the other oxides is 1: (0-35) but not 0, preferably 1 (4-6).
The mass ratio of the molybdenum oxide to the other oxide may be 1:1, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, 1:10, 1:11, 1:12, 1:13, 1:14, 1:15, 1:16, 1:17, 1:18, 1:19, 1:20, 1:21, 1:22, 1:23, 1:24, 1:25, 1:26, 1:27, 1:28, 1:29, 1:30, 1:31, 1:32, 1:33, 1:34, 1: 35.
In the present application, when the aqueous antibacterial disinfectant may be formed of water, molybdenum oxide and oxides of other elements, the pH of the aqueous antibacterial disinfectant is 1.5 to 3.5, preferably 1.6 to 2.5.
The pH of the aqueous antimicrobial disinfectant may be 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5.
When the aqueous antimicrobial disinfectant may be formed of water and molybdenum oxide, the pH of the aqueous antimicrobial disinfectant is 2.2 to 2.6, preferably 2.5.
In the present application, the content of molybdenum and/or other elements in the aqueous antimicrobial disinfectant is measured by using an X-ray fluorescence spectrometer (XRF).
Specific procedure for measurement with XRF: adding molybdenum oxide and other oxides into a flask, adding a proper amount of water, stirring and dissolving at a certain temperature, maintaining for a certain time, cooling, and filtering to remove solids to obtain the aqueous solution antibacterial disinfectant. And (4) dripping the antibacterial disinfectant on a glass dish, drying, taking out the dried powder by using a scraper, metering, and testing the element components in the powder by using XRF.
The application also provides a preparation method of the aqueous solution antibacterial disinfectant, which comprises the following steps:
the method comprises the following steps: adding molybdenum oxide and/or oxides of other elements into water, heating and stirring to dissolve the molybdenum oxide and/or oxides of other elements to form a mixed solution;
step two: cooling the mixed solution to cool the mixed solution to room temperature;
step three: and filtering the mixed solution cooled to room temperature to remove undissolved solid insoluble substances so as to obtain the aqueous solution antibacterial disinfectant.
The water content in step one is 3 to 35 times, preferably 20 times, the mass of the oxide of molybdenum oxide and/or other elements.
In the present application, the temperature for heating and dissolving is 50 ℃ to 130 ℃, preferably 90 ℃ to 110 ℃, and the heating and dissolving is maintained for 10min to 5h, preferably 2h to 5 h.
The molybdenum oxide and/or the oxide of another element may be dissolved at 50 ℃, 51 ℃, 52 ℃, 53 ℃, 54 ℃, 55 ℃, 56 ℃, 57 ℃, 58 ℃, 59 ℃, 60 ℃, 61 ℃, 62 ℃, 63 ℃, 64 ℃, 65 ℃, 66 ℃, 67 ℃, 68 ℃, 69 ℃, 70 ℃, 71 ℃, 72 ℃, 73 ℃, 74 ℃, 75 ℃, 76 ℃, 77 ℃, 78 ℃, 79 ℃, 80 ℃, 81 ℃, 82 ℃, 83 ℃, 84 ℃, 85 ℃, 86 ℃, 87 ℃, 88 ℃, 89 ℃, 90 ℃, 91 ℃, 92 ℃, 93 ℃, 94 ℃, 95 ℃, 96 ℃, 97 ℃, 98 ℃, 99 ℃, 100 ℃, 101 ℃, 102 ℃, 103 ℃, 104 ℃, 105 ℃, 106 ℃, 107 ℃, 108 ℃, 109 ℃, 110 ℃, 111 ℃, 112 ℃, 113 ℃, 114 ℃, 115 ℃, 116 ℃, 117 ℃, 118 ℃, 119 ℃, 120 ℃, 121 ℃, 122 ℃, 123 ℃, 124 ℃, 125 deg.C, 126 deg.C, 127 deg.C, 128 deg.C, 129 deg.C, 130 deg.C.
In the application, the cooling adopts natural cooling or other physical cooling modes to reach the room temperature.
The dissolution time of the molybdenum oxide and/or the oxide of other elements can be 10min, 20min, 30min, 40min, 50min, 60min, 70min, 80min, 90min, 100min, 110min, 120min, 130min, 140min, 150min, 160min, 170min, 180min, 190min, 200min, 210min, 220min, 230min, 240min, 250min, 260min, 270min, 280min, 290min, 300 min.
In the application, the filtration adopts polypropylene PP micro-filtration membrane with 2500 meshes to 12500 meshes, and preferably 12500 meshes.
The polypropylene PP microporous filtering membrane can be 2500 meshes, 3000 meshes, 3500 meshes, 4000 meshes, 4500 meshes, 5000 meshes, 5500 meshes, 6000 meshes, 6500 meshes, 7000 meshes, 7500 meshes, 8000 meshes, 8500 meshes, 9000 meshes, 9500 meshes, 10000 meshes, 10500 meshes, 11000 meshes, 11500 meshes, 12000 meshes and 12500 meshes.
The application provides an application of an aqueous solution antibacterial disinfectant in antibacterial coatings formed by water-based paints or in the antibacterial of metal, fabric, wood, ceramic and plastic surfaces.
The application provides an antibacterial disinfectant applied to the surfaces of metal, fabric, wood, ceramic and plastic, comprising the aqueous solution antibacterial disinfectant.
The antibacterial mechanism of the aqueous solution antibacterial disinfectant on the antibacterial coating on the surface of an object is as follows: after the surface antibacterial coating based on the hydrogen ion antibacterial mechanism is cured on the surface of an object, a layer of compact and cured reticular membrane can be formed on the surface of the object, the molybdenum oxide antibacterial agent embedded in the reticular membrane penetrates through the reticular membrane to carry out ionization reaction with water molecules outside the reticular membrane, the water molecules are decomposed into positively charged hydrogen ions which are uniformly distributed on the surface of the object to form a layer of weak acid microenvironment, and the rapid sterilization and the lasting antibacterial function are realized by virtue of multiple action mechanisms such as cation contact reaction, a fixing mechanism, biological sterilization and the like.
The application provides an antibiotic disinfectant of aqueous solution is used in the antibiotic mechanism that textile air bacterium strains the material: the molybdenum oxide antibacterial agent is fixed on the surface of a fiber material in a textile or a filter material by a special process, when air passes through the fibers of the filter material, molybdenum oxide antibacterial elements embedded on the surfaces of the fibers and water molecules in the air are subjected to ionization reaction, the water molecules are decomposed into positively charged hydrogen ions, the positively charged hydrogen ions are distributed in the filter material to form a three-dimensional weak acid microenvironment, and the rapid sterilization and lasting antibacterial functions are realized by virtue of multiple action mechanisms such as cation contact reaction, a fixing mechanism, biological sterilization and the like.
The application provides an application of an aqueous solution antibacterial disinfectant in disinfectant wet tissues, household special disinfectant, oral disinfectant, skin wound disinfectant, liquid dressing, vaginal lotion, public place disinfectant, hand disinfectant, textile surface disinfectant, skin disease disinfectant, washing products, fiber and gap article disinfectant.
When the aqueous solution antibacterial disinfectant is applied to the disinfectant wet tissue, the disinfectant wet tissue utilizes hydrogen ions for sterilization, has a wide antibacterial spectrum, has antibacterial effects on gram-positive bacteria, gram-negative bacteria, fungi and mold, and has the characteristics of no color, no odor, no irritation to skin, no toxicity, no corrosion and the like. Therefore, the wet tissue produced after the treatment of the aqueous solution antibacterial disinfectant can achieve a quick disinfection effect, does not mildew, and has a shelf life of two years.
When the aqueous solution antibacterial disinfectant is applied to the household special disinfectant, the household special disinfectant has the advantages of no toxicity, no color, no odor, no corrosion, wide bactericidal spectrum and the like, and is very suitable for household disinfection. But also can be used for sterilizing and cleaning melons, fruits and vegetables; the sterilizing and cleaning agent is used for sterilizing and cleaning various fabrics such as clothes, towels, bed sheets and the like; and can also be directly used for the disinfection and sterilization of the surfaces of objects such as furniture, carpets, sofas, kitchen utensils, sanitary wares and the like and air.
When the aqueous solution antibacterial disinfectant is applied to the oral disinfectant, the oral disinfectant has the advantages of no toxicity, no color, no odor, no corrosion, wide bactericidal spectrum and the like, and can be used for sanitary mouthwash.
The application discloses aqueous solution antibacterial disinfectant can make antibiotic liquid dressing, when using in superficial skin bacterium, fungi and virus infection and wound surface nursing, this product is hormone-free, colourless, nontoxic, nonirritant, noncorrosive, and the efficiency is lasting, so can be convenient be used for skin, wound surface, gynaecology and obstetrics, the washing and disinfecting of urology department.
The water solution antibacterial disinfectant can achieve satisfactory sterilization effect in a short time by only soaking or spraying for some medical supplies which cannot be sterilized at high temperature. The product can also be used for sterilizing air, wall and floor in sickroom.
When the aqueous solution antibacterial disinfectant is applied to vaginal lotion, lotion and gel disinfectant prepared by the product can be used for treating diseases such as bacterial, mycotic, trichomonas, senile and nonspecific vaginitis, cervicitis, vulvitis, pudendum pruritus and the like, can remove the peculiar smell of perineum, reduce secretion, form a layer of cation on the inner wall of the vagina for continuous and long-time bacteriostasis, and are suitable for cleaning and disinfecting the private parts before and after sexual intercourse, business trips, women menstrual period and the like, and prevent skin diseases and venereal diseases from infection and propagation. Meanwhile, the disinfectant is suitable for sterilizing and cleaning hands, feet, anus and other parts.
When the aqueous solution antibacterial disinfectant is applied to a public place sterilization purifying agent, a large amount of bacteria and viral infectious diseases seriously harm the life safety of human beings in the public place, and the sterilization and disinfection become an important link essential for maintaining the lives of people. The product has the characteristics of wide bactericidal spectrum, no toxicity, no color, no smell and the like, has no corrosiveness, and is very suitable for sterilization and disinfection of public places such as automobiles, trains, airplanes, ships, markets, hospitals, cinemas, hotels, restaurants and the like.
When the aqueous antibacterial disinfectant is applied to hand disinfectants, hand hygiene is closely related to the life of each person, about 80 percent of common infectious diseases are directly transmitted by both hands, and hand disinfection is obviously the most effective way for preventing and treating disease transmission. The product can be directly sprayed on hands as a hand disinfectant, and pathogenic bacteria on hands can be safely, effectively and conveniently removed at any time and any place. The product can effectively control the spread of typhoid fever, influenza, dysentery, pinkeye, gonorrhea and various skin diseases, and is suitable for restaurants, hotels, hospitals, markets, banks, schools, kindergartens, families, offices and travels. When the aqueous solution antibacterial disinfectant is applied to the textile surface disinfectant, the product can be used for developing antibacterial textiles and knitwear, such as towels, underwear, baby clothes, bedding articles, wool fabrics, gauze and the like. The textile is immersed into the special liquid for the product before the final finishing stage. When bacteria fall on the textile treated by the product, the active substances contained in the product are dissolved out by a trace amount of water, so that the bacteria are quickly killed, and the effects of antibiosis, moth-proofing, mildew resistance, no shrinkage and no hardening are achieved. The product can be conveniently developed into various aseptic and antibacterial sanitary towels, sanitary pads, baby diapers and the like, replaces other traditional disinfection modes such as high temperature and ethylene oxide and the like, not only reduces the cost, but also solves the problem of short validity period of the traditional disinfection mode. Since the product can be uniformly linked with the fine fibers of the above product, a polymer thin layer of the antibacterial agent is formed on the surface, and the optimum state after sterilization can be maintained while preventing secondary pollution. The product has stable performance and effective period up to two years, and can maintain the aseptic state of the produced sanitary towel and other products for a long time, and has obvious effects of cleaning female pudendum and preventing and treating gynecological diseases. When producing sanitary towels, sanitary protection pads and baby diapers, only solution with certain concentration is sprayed on the surfaces of the sanitary towels and the baby diapers, and then drying treatment is carried out.
The aqueous solution antibacterial disinfectant can be prepared into paste, and when the aqueous solution antibacterial disinfectant is applied to a dermatopathy disinfectant, the product has strong fungus killing effect and lasting effect, so that the aqueous solution antibacterial disinfectant can be conveniently used for treating dermatophytosis and tinea pedis caused by fungal infection, such as blister type, erosion type, scale keratinization type, desquamation type and the like; various fungal dermatoses such as tinea cruris, tinea capitis, tinea corporis, tinea manuum, etc. And has the effects of relieving itching, removing necrotic tissue, promoting granulation, and restoring normal function of skin.
When the aqueous solution antibacterial disinfectant is applied to washing articles, the washing articles with the disinfection function are generally added with a chlorine preparation as a disinfection component, and have the defects of corrosion to fabrics, fading, short sterilization period of validity, capability of being only used for white fabrics and the like. The product has the advantages of no toxicity, no color, no odor, no corrosion, no fading, no stimulation to skin mucosa, long effective period and the like, and can be used for developing high-tech environment-friendly disinfecting and sterilizing washing powder, washing liquid, dry cleaning agent and other products for washing fabrics with any color. The sterilization and disinfection become the essential important links in the daily life of people, and the product is published and has very wide market prospect. The product can kill various infectious germs on clothes and prevent the transmission of venereal diseases, and the washed clothes have remarkable antibacterial and mildewproof effects, and is especially important for children with an immaturity immune system, thereby playing a role in health protection. The product has strong antifungal effect, and can be used in shampoo for removing dandruff, tinea capitis caused by dandruff, seborrheic dermatitis, etc., and has remarkable antibacterial and antipruritic effects.
When the aqueous solution antibacterial disinfectant is applied to fiber and gap type article disinfectants, the aqueous solution antibacterial disinfectant can be used for antibacterial and mildew-proof treatment of cement antibacterial finishing agents, wood and paper. The air conditioner primarily filters the cotton, and the high-efficiency filter is used for antibacterial finishing. Antibacterial filter paper and antibacterial paper money. All surfaces of objects having fibers or voids can be used.
The water solution antibacterial disinfectant not only has antibacterial and disinfecting functions, but also is convenient to apply, can be conveniently applied to the surfaces of fabrics, woods, metals, ceramics and plastics, and still has the antibacterial function on the surfaces of the materials after drying. In the prior art, after the molybdenum oxide particles embedded in the plastic or the coating contact water, a weak acid environment is formed on the surface of an object, the surface of the object has antibacterial property, and the aqueous solution has no antibacterial property. And if the molybdenum oxide particle powder is directly put in water, the water still has no antibacterial property at normal temperature. In addition, tungsten oxide is dissolved in water according to the method of the present application, and the resulting aqueous solution remains without antimicrobial properties.
Examples
The experimental methods used in the following examples are all conventional methods, unless otherwise specified.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
Example 1
Adding 0.49g of molybdenum oxide (high-purity molybdenum trioxide produced by Europe tungsten molybdenum products Co., Ltd., Tazhou city, the content of which is 99.95%) and 6.42g of nanometer silicon oxide (New Material Co., Ltd., Xuancheng Jingrui, VK-SQ15, the average particle size is 30nm, and the specific surface area is 200 +/-25 square meters per gram) into a flask, adding 120g of water, stirring and dissolving at 85 ℃, maintaining for 180min, then cooling, and filtering to remove solids to obtain the aqueous solution antibacterial disinfectant. And (4) dripping the antibacterial disinfectant on a glass dish, drying, taking out the dried powder by using a scraper, metering, and testing the element components in the powder by using XRF. Specific parameters are shown in Table 1, below, columns 8 through 12.
Examples 2-9 and comparative examples 1-2 differ from example 1 in the ratio of molybdenum oxide to nanoscale silicon oxide, as well as in the dissolution temperature and holding time, and the specific parameters are shown in table 1.
Examples 10 to 11 differ from example 4 in the kind of other oxides, alumina in example 10 and titania in example 11, and the specific parameters are shown in table 1.
Example 12 differs from example 4 in that no other oxides are present and the specific parameters are given in table 1.
Example 13 differs from example 4 in the dissolution temperature, and the specific parameters are shown in table 1.
Example 14 differs from example 12 in the dissolution temperature, and the specific parameters are shown in table 1.
Example 15 differs from example 4 in that example 5 uses micron-sized silica.
Comparative example 3 is an aqueous antibacterial disinfectant of the prior art (84 disinfectant, manufactured by Shijiazhu Grett Riegie chemical Co., Ltd.).
Table 1 shows the parameters of examples and comparative preparation of aqueous antibacterial disinfectant solutions
Figure BDA0002642559330000111
Test examples
1. Bacteriostasis test
The water solution antibacterial disinfectant adopts a suspension quantitative method to carry out a bacteriostasis test. The test bacteria are selected from Escherichia coli and Staphylococcus aureus with concentration of 5.0 × 105CFU/mL~4.5×106CFU/mL of bacterial suspension. Phosphate Buffered Saline (PBS) (pH7.2-7.4) concentration: 0.03 mol/L. The experimental steps are as follows: 5.0mL of each sample (the aqueous antibacterial disinfectant prepared in example 1-example 15 and comparative example 1-comparative example 2, and the antibacterial agent in comparative example 3) was added to each of 19 sterile centrifuge tubes, and the mixture was placed in a water bath at 20 + -1 ℃ for 5min, followed by addition of 0.1mL of the test bacterial suspension (the test bacterial suspension was prepared with the test bacteria at a certain concentration), rapidly mixed, and immediately timed. The test bacteria interacted with the sample for 15 min. Then 0.01mL of test bacterium and sample mixed liquid is respectively sucked and inoculated into 1 plate, whether bacteria on the culture medium are produced or not is observed after 48 hours of culture, and whether the bacteriostatic effect exists or not is judged, and the details are shown in Table 2.
Table 2 shows the performance parameters of the aqueous antibacterial disinfectant prepared in each example and comparative examples, the bacteriostatic activity of Escherichia coli
Figure BDA0002642559330000121
Figure BDA0002642559330000131
Staphylococcus aureus antibacterial activity
Figure BDA0002642559330000132
2. Sterilization test
The aqueous solution antibacterial disinfectant adopts a suspension quantitative method for sterilization test. The test bacteria are selected from Escherichia coli and Staphylococcus aureus with concentration of 5.0 × 105CFU/mL~4.5×106CFU/mL of bacterial suspension. Neutralizer (0.2% lecithin + 3.0% tween 80+ 0.1% sodium thiosulfate in PBS): the experimental steps are as follows: 5.0mL of each of the samples (the aqueous antibacterial disinfectant prepared in examples 1 to 15 and comparative examples 1 to 2, and the antibacterial agent prepared in comparative example 3) was added to each of 19 sterile centrifuge tubes, and the mixture was placed in a water bath at 20. + -. 1 ℃ for 5 minutes, followed by addition of 0.1mL of the test bacterial suspension, followed by rapid mixing and immediate timing. The test bacteria and the sample interact for 15min, respectively sucking 0.5mL of the mixed solution of the test bacteria and the antibacterial agent, adding the mixed solution into 4.5mL of the neutralizer, and uniformly mixing. After the test bacteria and the antibacterial agent mixed liquor of each tube acts for 10min through a neutralizing agent, 0.01mL of test bacteria and sample mixed liquor of each tube is respectively sucked and inoculated on 1 plate, and then the plate is placed in a constant-temperature incubator at the temperature of 37 ℃ for preservation and culture for 48 h. The bactericidal properties were judged by observing the growth of the bacteria on the medium, as detailed in table 3.
Table 3 shows the performance parameters of the aqueous antibacterial disinfectant prepared in each example and comparative example, the bactericidal activity of Escherichia coli
Figure BDA0002642559330000141
Staphylococcus aureus bactericidal activity
Figure BDA0002642559330000142
Figure BDA0002642559330000151
And (3) knotting: the above table shows that the aqueous solution antibacterial disinfectant has short action time and strong bacteriostatic and bactericidal effects, and the antibacterial rate can reach 99.9%.
3. Antibacterial property
The aqueous solution antibacterial disinfectant is applied to fabrics such as cotton cloth, non-woven fabric and the like, and after drying, the antibacterial performance is tested by the following method.
Culturing Escherichia coli or Staphylococcus aureus to obtain a culture solution with a concentration of 5.0 × 105CFU/mL~ 4.5×106CFU/mL concentration of bacteria-containing solution. The same amount of the bacterial solution was dropped on the surfaces of the fabrics to which the aqueous antibacterial disinfectant of examples 1 to 15 and comparative examples 1 to 3 of the present application was applied and the control fabrics, respectively. At the specified sampling time point, taking out the culture medium by using a sampler, eluting the culture medium by using eluent, uniformly coating the culture medium on a culture dish by absorbing the eluent, and then placing the culture medium in a constant temperature incubator at the temperature of 37 ℃ for preserving and culturing for 48 hours. The bactericidal performance was judged by observing the growth of the bacteria on the medium, with the performance parameters shown in table 4.
Table 4 shows the performance parameters of the aqueous antibacterial disinfectant prepared in each example and comparative example on the surface of fabrics such as non-woven fabrics, cotton fabrics and the like.
Staphylococcus aureus
Figure BDA0002642559330000152
Figure BDA0002642559330000161
And (3) knotting: the above table shows that the aqueous solution antibacterial disinfectant has a strong antibacterial effect, and the bacteriostasis rate can reach 99.9%.
4. Acute oral toxicity test
Test animals: 20 KM mice (male and female halves, around 20 g), SPF grade, provided by southern medical university, license number: SCXK (Yue) 2016-; quality certification number: 440021000235812.
detecting the environment: shielding the environment at the temperature of 20-26 ℃; relative humidity of 40% -70%, license number: SYXK (Yue) 2018-.
The feed source is as follows: guangdong province medical laboratory animal center; producing license numbers: guangdong syndrome (2019) 05073; the production date is as follows: 2019-12-02.
Sample preparation: 6.32g of a sample (the aqueous antibacterial disinfectant prepared in example 4) was weighed, and purified water was added to prepare 25mL of a sample solution.
The test method comprises adopting one-time maximum test, fasting overnight before test, keeping water ー times and 5056mg/kg weight dose, and continuously fasting for 3 hr after contamination. Animals were observed daily for a4 consecutive days. Once a week, the dead animals and the living animals were examined for gross dissection after the end of the observation.
And (3) test results: the infected animals have no toxic symptoms and dead animals have no abnormal body weight within 14 days of infection, and the general anatomy of the animals after the experimental observation is finished is not abnormal, and the details are shown in a table 4.
Table 4 shows the acute oral toxicity test of the aqueous antibacterial disinfectant prepared in example 4
Figure BDA0002642559330000171
And (3) knotting: as can be seen from the above table, oral LD of KM mice with the aqueous antibacterial disinfectant prepared in example 4 of the present application50>5000mg/kg body weight, rootAccording to the evaluation regulation of 2.3.1 acute oral toxicity test in disinfection technical Specification (2002 edition), the oral toxicity test is actually nontoxic. The aqueous antimicrobial disinfectant described herein is therefore non-toxic.
5. Mutagenesis test (mouse bone marrow pleochromocyte micronucleus test)
Test animals: 50 KM mice (male and female halves, about 26 g), SPF grade, supplied by southern medical university, license number: SCXK (Yue) 2016-; quality certification number: 400210003613
Detecting the environment: shielding the environment at the temperature of 20-26 ℃; relative humidity 409% -70%, license number: SYXK (Yue) 2018-.
The feed source is as follows: guangdong province medical laboratory animal center; producing license numbers: guangdong syndrome (2019) 05073; the production date is as follows: 2020.01-03.
Positive control: cyclophosphamide (40mg/kg body weight, brand: Aike reagent, lot: 201906151).
Negative control: pure water.
And (3) testing a sample: example 4 preparation of an aqueous antimicrobial disinfectant
A test object group, wherein the concentration of a prepared test sample is as follows: 500mg/kg, 2000mg/kg and 5000mg/kg of body weight were prepared with pure water.
The test method comprises the following steps: adopts a method of oral gavage for 30h contamination, and the interval between two times of contamination is 24 h. Animals were sacrificed 6h after the second exposure by cervical dislocation, femurs were removed and the medullary cavity was flushed with calf serum. Smear, fix, stain, and examine with washing solution. Statistical analysis was performed with SPSS.
And (3) test results: compared with the negative control group, the number of the micronucleus-containing pleochromocyte in the bone marrow of the mice of the positive control group is obviously increased (P <0.05), while the micronucleus rate of the pleochromocyte of each test animal group is compared with that of the negative control group, the difference is not statistically significant (P >0.05), and the details are shown in a table 5.
Table 5 shows mutagenesis test of the aqueous antibacterial disinfectant prepared in example 4
Figure BDA0002642559330000181
Note: PCE: pleochromophilic red blood cell
Micronucleus cell rate (‰) and PCE/NCE were counted in mice as mean standard deviation.
And (3) knotting: as can be seen from the above table, the aqueous antibacterial disinfectant has no significant difference in the micronucleus rates of the erythrocytes in the myeloeosinophilic micronucleus test of the mice compared with the negative control group under three administration doses of 500mg/kg, 2000mg/kg and 5000mg/kg of body weight. Therefore, according to the evaluation of the myelopleochromocyte micronucleus test in mice, 2.3 and 8.4 in the technical Specification for Disinfection (2002 edition), the test sample showed no in vivo chromosome-damaging effect on KM mice at three doses of 500mg/kg, 2000mg/kg and 5000mg/kg body weight.
6. One complete skin irritation test
Test animals: 3 New Zealand rabbits (female, about 2.2 kg), provided by the Longguixing animal farm in the white cloud area, Guangzhou, license number: SCXK (yue) 2017-; quality certification number: 44817200000593.
Detecting the environment: common environment, temperature 20-26 ℃, relative humidity 40-70%, license number: SYXK (Yue) 2018-.
The feed source is as follows: guangdong province medical laboratory animal center; producing license numbers: guangdong syndrome (2019) 05073; the production date is 2020-02-10.
Sample preparation: the aqueous antibacterial disinfectant prepared in example 4 was used.
The test method comprises the following steps: about 24 hours before the test, the hairs on both sides of the spine of the test animal are shaved off without damaging the epidermis, and the hair removal range is about 3cm multiplied by 3cm on the left and right sides respectively. 0.5mL of the test substance was dropped onto the shaved skin on the left side of an area of 2.5cm by 2.5cm, covered with two layers of gauze and a plastic film, and fixed with a non-irritating adhesive tape. The other side of the skin served as a control. After 4h of action, the test substance is removed by digestion with warm water. Skin reactions were observed at 1h, 24h, 48h after removal of the test substance and scored.
The test results are detailed in table 6.
Table 6 shows one complete skin irritation test of the aqueous antimicrobial disinfectant prepared in example 4
Figure BDA0002642559330000191
And (3) knotting: as can be seen from the above table, the highest mean value of the integral of each observation time point of the aqueous antibacterial disinfectant described in example 4 of the present application on a complete skin irritation test of new zealand rabbits was 0, and thus the aqueous antibacterial disinfectant described in the present application was non-irritant according to the skin irritation intensity classification of the skin irritation test of disinfection specification (2002 edition).
While embodiments of the present application have been described above in connection with specific embodiments thereof, the present application is not limited to the above-described embodiments and fields of application, which are intended to be illustrative, instructive, and not restrictive. Those skilled in the art, having the benefit of this disclosure, may effect numerous modifications thereto and changes may be made without departing from the scope of the invention as defined by the appended claims.

Claims (26)

1. An aqueous solution antibacterial disinfectant is characterized by being formed by water, molybdenum oxide and oxides of other elements, wherein the content of molybdenum element in the aqueous solution antibacterial disinfectant is 0.1-0.9 wt%, and the content of the other elements is 0-0.2 wt%; the oxide of the other element is silicon oxide.
2. The aqueous antibacterial disinfectant according to claim 1, wherein the content of molybdenum element in the aqueous antibacterial disinfectant is 0.3wt% to 0.5wt%, and the content of other elements is 0.005wt% to 0.02 wt%.
3. An aqueous antimicrobial disinfectant according to claim 1 wherein said oxide of another element is nano-sized silica;
purity of the nano-scale silicon oxideThe degree is 99-99.9%, the average particle diameter is 5-90nm, the specific surface area is 100-2/g。
4. An aqueous antibacterial disinfectant according to claim 3 wherein said nano-sized silica has a purity of 99.8%, an average particle size of 30nm and a specific surface area of 200 ± 25m2/g。
5. The aqueous antibacterial disinfectant as set forth in claim 1, wherein the mass ratio of said molybdenum oxide to said oxide of other element is 1: (0-35) but does not include 0.
6. The aqueous antibacterial disinfectant as set forth in claim 1, wherein the mass ratio of said molybdenum oxide to said oxide of said other element is 1 (4-6).
7. An aqueous antimicrobial disinfectant according to claim 1 wherein said aqueous antimicrobial disinfectant has a pH of from 1.5 to 3.5.
8. An aqueous antimicrobial disinfectant according to claim 1 wherein said aqueous antimicrobial disinfectant has a pH of from 1.6 to 2.5.
9. An aqueous antibacterial disinfectant according to claim 1 wherein the content of molybdenum and/or other elements in said aqueous antibacterial disinfectant is measured by using an X-ray fluorescence spectrometer.
10. A preparation method of an aqueous solution antibacterial disinfectant is characterized by comprising the following steps:
adding molybdenum oxide and oxides of other elements into water, heating and stirring to dissolve the molybdenum oxide and the oxides of the other elements to form a mixed solution;
the mixture was then cooled to cool the solution to room temperature;
filtering the mixed solution cooled to room temperature to remove undissolved solid insoluble substances so as to obtain the aqueous solution antibacterial disinfectant;
the oxide of the other element is silicon oxide;
the content of molybdenum element in the aqueous solution antibacterial disinfectant is 0.1-0.9 wt%, and the content of silicon element is 0-0.2 wt%.
11. The method as claimed in claim 10, wherein the water is contained in an amount of 3 to 35 times the amount of the oxides of molybdenum oxide and other elements.
12. The method as claimed in claim 10, wherein the water is contained in an amount of 20 times the amount of the oxides of molybdenum oxide and other elements.
13. The method for preparing an aqueous antibacterial disinfectant as claimed in claim 10, wherein the temperature for heating and dissolving is 50 ℃ to 130 ℃ for 10min to 5 h.
14. The method for preparing an aqueous antibacterial disinfectant as claimed in claim 10, wherein the temperature for heating and dissolving is 90-110 ℃ for 2-5 h.
15. The method for preparing an aqueous antibacterial disinfectant according to claim 10, wherein said cooling is carried out by natural cooling or other physical cooling means to room temperature.
16. The method for preparing an aqueous antibacterial disinfectant as claimed in claim 10, wherein said filtering is performed by polypropylene PP microfiltration membrane with 2500 to 12500 mesh.
17. The method for preparing an aqueous antibacterial disinfectant as claimed in claim 10, wherein said filtering is performed by using 12500 mesh polypropylene (PP) microfiltration membrane.
18. The method of claim 10, wherein the oxide of the other element is nano-scale silicon oxide;
the purity of the nano-grade silicon oxide is 99-99.9%, the average particle size is 5-90nm, the specific surface area is 100-2/g。
19. The method as claimed in claim 18, wherein the nano-sized silica has a purity of 99.8%, an average particle diameter of 30nm, and a specific surface area of 200 ± 25m2/g。
20. The method as claimed in claim 10, wherein the content of molybdenum in the aqueous antibacterial disinfectant is 0.3wt% to 0.5wt%, and the content of other elements is 0.005wt% to 0.02 wt%.
21. The method of claim 10, wherein the mass ratio of the molybdenum oxide to the oxide of the other element is 1: (0-35).
22. The method for preparing an aqueous antibacterial disinfectant as claimed in claim 10, wherein the mass ratio of said molybdenum oxide to said oxide of said other element is 1 (4-6).
23. The method of claim 22, wherein the aqueous antimicrobial disinfectant has a pH of 1.5 to 3.5.
24. The method of claim 22, wherein the aqueous antimicrobial disinfectant has a pH of 1.6 to 2.5.
25. Use of an aqueous antimicrobial disinfectant according to any one of claims 1 to 9 or prepared by the process of any one of claims 10 to 24 for the antimicrobial coating of aqueous coatings or for the antimicrobial treatment of metal, textile, wood, ceramic, plastic surfaces.
26. An antibacterial disinfectant for application to metal, textile, wood, ceramic, plastic surfaces, comprising an aqueous antibacterial disinfectant according to any one of claims 1 to 9 or prepared by the preparation method of any one of claims 10 to 24.
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