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CN106538583B - Long-acting disinfection bactericidal composition, its coating method and the regeneration method for coating - Google Patents

Long-acting disinfection bactericidal composition, its coating method and the regeneration method for coating Download PDF

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Publication number
CN106538583B
CN106538583B CN201610923330.7A CN201610923330A CN106538583B CN 106538583 B CN106538583 B CN 106538583B CN 201610923330 A CN201610923330 A CN 201610923330A CN 106538583 B CN106538583 B CN 106538583B
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coating
substrate
bonding agent
composition
long
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Expired - Fee Related
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CN201610923330.7A
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Chinese (zh)
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CN106538583A (en
Inventor
刘成龙
王天桃
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Jiangsu Grams Of Micro Nano Science And Technology Co Ltd
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Jiangsu Grams Of Micro Nano Science And Technology 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
    • A01N47/00Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/40Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having a double or triple bond to nitrogen, e.g. cyanates, cyanamides
    • A01N47/42Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having a double or triple bond to nitrogen, e.g. cyanates, cyanamides containing —N=CX2 groups, e.g. isothiourea
    • A01N47/44Guanidine; Derivatives 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
    • A01N25/04Dispersions, emulsions, suspoemulsions, suspension concentrates or gels
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B05SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05DPROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/002Pretreatement
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B05SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05DPROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/007After-treatment
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B05SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05DPROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D5/00Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • 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

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  • Life Sciences & Earth Sciences (AREA)
  • Plant Pathology (AREA)
  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • General Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Zoology (AREA)
  • Pest Control & Pesticides (AREA)
  • Dentistry (AREA)
  • Agronomy & Crop Science (AREA)
  • Environmental Sciences (AREA)
  • Toxicology (AREA)
  • Dispersion Chemistry (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Paints Or Removers (AREA)

Abstract

The present invention relates to a kind of long-acting disinfection bactericidal compositions, the composition is to form the sol-gel coating fluid of antimicrobial membranes in substrate surface, composition includes fungicide, bonding agent, curing agent, stabilizer, solvent and water, fungicide is set to be linked to substrate surface by the bonding agent, after coating is applied to substrate, stabilizer and solvent can volatilize, and so that bonding agent is formed a film by curing agent, and the thickness of film is adjusted by the concentration and dosage of solvent;Fungicide is that polyguanidine, polyguanidine salt or its mixing salt, bonding agent are organosilicon or organosilicon and the organic molecule added based on the use of the coating and function.Even invention significantly improves the biocide sustainable time for acting on matrix and the biocides of antimicrobial effect very small part.

Description

Long-acting disinfection bactericidal composition, its coating method and the regeneration method for coating
Technical field
The antimicrobial colloidal sol-for being covered on substrate surface is capable of forming the present invention relates to the coating fluid for being applied to substrate surface Gel coat.In addition, the present invention relates to the method being used to form on antimicrobial colloidal sol-gel coat to substrate, Yi Jiyong In the method for the antimicrobial acivity of the coating of regeneration substrate surface.
Background technique
A variety of object table cleanings and formation top coat are to make to have antimicrobial effect to be convenient and very heavy It wants, such as hospital, food industry, public food and beverage sevice and in fields such as different communal facilitys.In the past, table easy to clean Face is all the coating by using low-surface-energy, such as passes through different fluorine compounds, (PTFE, Teflon) wax organosilicon.This Through a long time is applied in various coating the compound of a little enhancing cleannes effects.Various active constituents, such as kill livestock Agent silver, titanium oxide, which is also added to, to be used to provide eliminating bacteria and the property of other microorganisms in coating.
However, paint type coating is limited the applicability of various materials.In general, coating be substantially it is opaque, And they change the form and property of body surface to be smeared.In many cases, thick, film-form painting feed liquid is added The requirement that the quality and quantity of agent are limited, such as when biocide is used.Required cleannes and antimicrobial Effect often still can be insufficient, because coated film has covered active material therein, prevents biocide from playing completely Effect or effect are difficult to persistently.And for a kind of coating of effective smear type, additive usually requires very more amounts, Increase the complexity and preparation cost of raw material.
In order to eliminate the microorganism of body surface, a variety of disinfectants added with fungicide can also be used.Routine disinfection It is all often disposably that, although their disinfections are good, action time is very of short duration, it cannot for a long time effectively.
It is lighter to the pollution level of substrate surface, and be to apply to the simplification and antibiotic property of contaminated surface cleaning capacity Property necessary to layer.In addition, the coating used must be wear-resisting as far as possible and provides the guarantor for avoiding microbial contamination as long as possible Shield, and the characteristic of substrate surface cannot be changed.
Summary of the invention
The object of the invention is to come to provide a kind of antimicrobial coating so that the coating is suitable for various material Substrate surface sterilization, which is that composition is formed in a manner of sol-gel, product clear, colorless have it is not noticeable and Long-acting lasting feature, and the original property of substrate surface is maintained, there is coating oleophobic, hydrophobic property to improve object simultaneously The cleannes on surface, while can also make substrate surface that there is long-acting anti-microbial effect.
The present invention solves the above problems used technical solution are as follows: a kind of long-acting disinfection bactericidal composition the composition is The sol-gel coating fluid of antimicrobial membranes is formed in substrate surface, composition includes fungicide, bonding agent, curing agent, stabilization Agent, solvent and water make fungicide be linked to substrate surface by the bonding agent, after coating is applied to substrate, stabilizer and Solvent can volatilize, and so that bonding agent is formed a film by curing agent, and the thickness of film is adjusted by the concentration and dosage of solvent;The sterilization Agent be polyguanidine, polyguanidine salt or its mix salt, the bonding agent be organosilicon or organosilicon with based on the coating use and Function is come the organic molecule that adds.
The effect of the invention floating coat be based on suitable sol- gel coating and apply active antimicrobial components or The interaction of fungicide, thus significantly improving biocide sustainable time for acting on matrix and antimicrobial Even the biocide of effect very small part.Sol- gel coating is after being applied to substrate surface, bonding agent therein A coat side relative to substrate is formd, solvent volatilization, under the action of solidifying the catalyst such as stable, bonding agent forms one Layer hyaline membrane, and polyguanidine salt of the chemical bonds as sterilization Antibacterial Constituents, and such as by the suitable bonding agent of selection Organ of luorosilane, allows film while the characteristic that has oleophobic hydrophobic, because and there is clean effect, and to substrate surface no property Change and pattern influences.
Preferably, polyguanidine of the invention is poly hexamethylene biguanide (PHMG), and CAS code name is 57028-96-3, PHMG Molecular weight change from 8000 to 10000, which contains many active sites with cell film reaction.Polyguanidine salt is poly- The mixture of hexa-methylene guanidine phosphate or poly (hexamethylene) hydrochloride or two class salt.
Based on antimicrobial effect and use, the content of the antimicrobial components in coating can be different.Cause For antimicrobial reagent can be formed into coating surface, even the antimicrobial reagent of very little metering can also mention For permanently effective anti-microbial effect.In addition, PHMG is a kind of effective antimicrobial, it is also due to this original in this way Cause will provide for a permanently effective antibacterial action low dose to resist such as Gram-negative and Gram-positive Bacterium, fungi, bacterium, virus, yeast and mold.The validity of PHMG is based on him with positive charge, can with it is negatively charged Microbial film reaction, thus destroying cells film.The mechanism of action of PHMG is physics rather than chemical action, and belonging to safety has The antimicrobial of hypotoxicity has very wide application range.PHMG has antimicrobial work under drying and wet environment Property.
Based on above-mentioned action principle, fungicide dosage of the invention is more saved, in coating fluid, cosmocil stearate Content is from 0.1% to relative to 40% in conjunction with agent content.Best, the concentration of PHMG is the weight of 1~15% bonding agent.It is applying In material, the matrix that this water-soluble antibacterial components is connected to bonding agent generation is connected to the surface of substrate with this.
Preferably, the bonding agent is silicon fluoride.It forms a hydrophobic surface on base the earth's surface, wherein can be formed One is easier clean anti-pollution layer.
Above-mentioned organic molecule is selected from acrylate, epoxy resin, vinyl esters and polyurethane, in order to form a film or have film There is characteristic, such as stablizes, cleaning, smooth, scratch resistance.
Preferably, curing agent is ethylenediamine.
Preferably, stabilizer is glacial acetic acid, when this coating fluid not being coated on substrate surface, can prevent PHMG and curing agent It reacts, can volatilize naturally after being coated on substrate surface, and then promote film formation reaction.
Preferably, the solvent is the isopropanol of 1:1 volume ratio and the mixed liquor of ethyl alcohol.
The coating method of long-acting disinfection bactericidal composition of the present invention: the sol-gel coating fluid is especially suitable for can be The substrate of covalent metal oxygen key, especially stainless steel and ceramics and glass surface are formed between substrate;And for cannot be direct The surface of attachment has to by being processed into the suitable state of chemical property, including plastics and coating then need to carry out corresponding table Face pretreatment;The composition is also suitable for using on porous surface, and composition will be partially absorbed substrate to be coated It is interior, but still lasting and uniform film can be formed in substrate surface.
Before the coating, substrate is pre-processed, the pretreatment is that substrate is instigated to obtain necessary processing and property Matter, the quantity including reduction pollutant to acceptable level, to realize steady and flawless colloidal sol-gel coat, to The surface of coating must be clean;Or it is suitable for forming a film by the physicochemical properties of cleaning modification substrate surface, and swash With intensified response, the pretreatment is necessary otherwise influences the property of coating on surface living, but can be significantly in the coating of coating, bonding Property and durability.
The composition can be applied in substrate by way of cleaning, brushing, spraying, stranding, dipping and form coating, apply Layer is dried at room temperature for and solidifies, and coating drying time is differed from a few minutes to a few houres, this depends on the pre- of substrate surface Processing whether and mode, in a hard and smooth substrate surface, coating can dry faster compared on perforated substrate.
Long-acting disinfection bactericidal composition of the invention can be used for the regeneration update method to base coating: the coating fluid can be with Apply in the substrate surface having been coated with without clearing up old coating, new coating, which will adhere to, to be ground off or become more In the hole mechanically or chemically worn in hole, old coating can easily update: in normal cleaning process;Come again, The antimicrobial acivity of coating can be by using the composition including at least one polyguanidine salt as antibacterial active constituents, to fill The porous or wearing part of old coating updates again, and old coating on the surface of the substrate do not need as colloidal sol of the invention Gel coat, new coating, which can be, is formed by coating either any updated coating of coating by sol-gel method.
Compared with the prior art, the advantages of the present invention are as follows:
(1) fungicide/antimicrobial used in coating is polyguanidine salt either its mixing salt, utilizes its band There are the antibacterial characteristics of charge.The preferred cosmocil stearate of the present invention (PHMG), by bonding agent, water-soluble PHMG can To be kept for a long time in substrate surface, rather than the membranaceous coating of thickness reality.In this way, the anti-microbial effect of PHMG It is maintained on coating, even if the only amount of very small part.In other words, thin layer collosol and gel coating fluid according to the present invention It has fixed fungicide itself but not has influenced its antibacterial action.In this way, even there was only minimal amount in stromal surface Fungicide it is also ensured that effectively, long-acting anti-microbial properties.The antibacterial action of coating of the present invention is dry and humidity Under the conditions of it is all effective, this be combined with bonding agent characteristic realize.
(2) coating fluid of the invention can be easy to be applied to substrate to be coated.The bonding agent of coating is attached to base In the material at bottom.If the chemical property of substrate, which is suitable, or substrate is processed has suitable chemical property.Altogether Valence metal-oxygen key can be formed between coating and base material.Particularly, relative to substrate, the guide frame of bonding agent can also make Bonding agent forms the coating of hydrophobic oleophobic, and coating is made to have the advantages that anti-pollution and easy cleaning.
(3) organosilan (silicon fluoride) and PHMG reaction, so that substrate surface forms positively charged mesh nanometer film, hold very much It is easily adsorbed in electronegative all kinds of bacteriums, virus, to inhibit the splitting function of bacterial virus, it is made to lose fecundity Power makes the rapid death by suffocation of microorganism in addition the film that polymer is formed plugs the respiration channel of microorganism.Belong to physics side The sterilizing of formula.This mode will not generate the drug resistance bacterium of hereditary variation, to realize physical antibacterial efficiently, permanent, safe Effect.After film forming, the physical and chemical performance of film is sufficiently stable, therefore bactericidal effect is influenced pole by environment temperature, pH and organic matter etc. It is small.
Coating of the invention can be good at being attached on stainless steel and other metals, glass, various ceramic surfaces, and not Cracky is degenerated.The coating also can be used in painted surface and plastic material.Substrate surface can also pre-process before coating, For improving the adhesiveness of coating fluid.
Specific embodiment
Present invention is further described in detail with reference to embodiments.
The long acting antibiotic composition of the present embodiment is a kind of sol-gel coating fluid, can be widely applied to need to remove The all trades and professions of bacterium, and coating can be shifted easily as new purposes.Based on the antibacterial agent of the application in dry and tide The fact that greater activity is kept under conditions of wet, with having widened coating fluid use scope.The coating also can be applied to complexity The surface of shape.
Especially hospital and food industry are very favorable using the coating fluid of the present embodiment.Within the hospital, coating is made To need antimicrobial protection, including used on wall, door, floor and various furniture and all surface of equipment.In food In industry, improve as further, for example, the shelf-life of food, because the food in preparation and treatment process is not exposed to Thus microorganism can also reduce addition of the preservative in food.In processing industry, coating can be used for coating any production Facility and manufacturing machine.The coating fluid can also be used for the software package by plastics or pressboard coating.In addition, the coating fluid can answer extensively For food and beverage sevice, school, day-care center, communal facility, office and hot spring.Furthermore any ceramic surface, example be can be applied to Such as, in sanitary installations such as bathrooms.It can also be coated on wood surface, in other words, coating may be used as timber preservative.
Multiple groups test prove the coating be it is effective, it is wieldy, be suitable for large surface and use.Coating of the invention It can be used in ventilating system, to prevent microbial contamination.The various purifications for water are also that can be used, safe nothing Poison.
In following example, for its effect, be not steel surface and in hospital environment bacterium on coating Quantity is detected.Uncoated stainless steel surface is used as referring to.
The bacterium bacterial strain used in testing is methicillin-resistant staphylococcus aureus strains A TCC 33591 and verdigris Pseudomonad strain ATCC 15442(is only in humid conditions).
In test coating solution used, by mass percentage, including PHMG 0.016% as it is antimicrobial at Point, for 0.3% silicon fluoride as bonding agent, 5% ethylenediamine, glacial acetic acid 1.7% and water 5%, rest part is by the different of 1:1 volume ratio The mixed liquor of propyl alcohol and ethyl alcohol.
Stainless steel surface is handled and is dried with above-mentioned coating solution.These tests are in two dry tack frees and moist table Face carries out.Uncoated stainless steel surface is normally used as reference.
The test is carried out by application 13697 surface disinfectant standard of EN.It is in viability assays, 100 μ l are micro- On the surface that the mixture of biological solution (1 × 10 PMY/ milliliters of<5>) is moved to, is dried 2 hours at 37 DEG C and sampling exists On culture medium (before dry), 4h, for 24 hours, 48 hours after liquid relief.A part of stainless steel surface be stored in dry condition Under a series of tests of (+37 DEG C) in humid conditions of (room temperature) and another part time.Two parallel samples are surveyed Examination.Sample is kept the temperature 1 day at 37 DEG C.
In testing, it is found that the coating significantly reduces MRSA and the bacterium of Pseudomonas aeruginosa is dense on stainless steel surface Degree.Difference between coating and uncoated steel is that all there were significant differences under drying and wet condition.The result of the test is shown in Table 1 and 2.
The disinfecting, antimicrobial composition of the above experiment results proved, the present embodiment has preferable sterilization antibacterial ability to bacterium, And whether dry or wet environment, effect duration is long, and coating is firmly combined in stainless steel surface, the work to fungicide Property ingredient keep good.
In addition to the implementation, all to use equivalent transformation or equivalent replacement the invention also includes there is an other embodiments The technical solution that mode is formed should all be fallen within the scope of the hereto appended claims.

Claims (4)

1. a kind of long-acting disinfection bactericidal composition, it is characterised in that: the composition is to form antimicrobial membranes in substrate surface Sol-gel coating fluid, composition include fungicide, bonding agent, curing agent, stabilizer, solvent and water, and the stabilizer is ice Acetic acid makes fungicide be linked to substrate surface by the bonding agent, and after coating is applied to substrate, stabilizer and solvent can be waved Hair, makes bonding agent form a film, the thickness of film is adjusted by the concentration and dosage of solvent by curing agent;The fungicide is poly- Guanidine, polyguanidine salt or its mix salt, the bonding agent be silicon fluoride or silicon fluoride with based on the coating use and function come The organic molecule of addition;
The polyguanidine be poly hexamethylene biguanide, molecular weight be 8000~10000, polyguanidine salt be polyhexamethylene guanide phosphate or The mixture of poly (hexamethylene) hydrochloride or two class salt;
The organic molecule is selected from acrylate, epoxy resin, vinyl esters and polyurethane;
The curing agent is ethylenediamine.
2. long-acting disinfection bactericidal composition according to claim 1, it is characterised in that: the solvent is 1:1 volume ratio The mixed liquor of isopropanol and ethyl alcohol.
3. the coating method of long-acting disinfection bactericidal composition according to claim 1, it is characterised in that:
The composition is suitable for be formed the substrate of covalent metal oxygen key between substrate;And the table for cannot directly adhere to Face has to by being processed into the suitable state of chemical property;The composition is also suitable for using on porous surface, composition It will be partially absorbed in substrate to be coated, but still lasting and uniform film can be formed in substrate surface;
Before the coating, substrate is pre-processed, the pretreatment is that substrate is instigated to obtain necessary processing and property: being subtracted The quantity of of low pollution object is to acceptable level, to realize steady and flawless colloidal sol-gel coat, surface to be coated It must be clean;
The composition can be applied in substrate by way of cleaning, brushing, spraying, stranding, dipping and form coating, and coating exists It is dry at room temperature and solidify, coating drying time from a few minutes to a few houres, whether this depends on the pretreatment of substrate surface And mode, in a hard and smooth substrate surface, coating can dry faster compared on perforated substrate.
4. the coating method of long-acting disinfection bactericidal composition according to claim 3, it is characterised in that: the substrate is not Become rusty steel and ceramics and glass surface.
CN201610923330.7A 2016-10-29 2016-10-29 Long-acting disinfection bactericidal composition, its coating method and the regeneration method for coating Expired - Fee Related CN106538583B (en)

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CN108441080A (en) * 2018-04-25 2018-08-24 上海嘉柏丽实业有限公司 A kind of pseudo-classic floor coatings of aqueous inorganic
CN109354912A (en) * 2018-11-07 2019-02-19 温州莲华环保科技有限公司 A kind of medical bag protective film and its manufacture craft
CN111574871B (en) * 2020-04-23 2021-07-23 武汉中科先进技术研究院有限公司 Modified fluorosilane composite sol, preparation method thereof, coating containing modified fluorosilane composite sol, and preparation method and application of coating
CN111642437B (en) * 2020-05-09 2021-08-20 中国水产科学研究院东海水产研究所 Preparation method of truncated cone-shaped side net for semi-submersible type culture platform
CN111500137B (en) * 2020-05-18 2022-12-20 刘白玲 Antibacterial and antiviral emulsion adhesive film-forming agent, preparation method and application thereof
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US20220071216A1 (en) * 2020-09-08 2022-03-10 The Hong Kong University Of Science And Technology Disinfectant-dosing microgel and method of using the same
CN113712028A (en) * 2020-10-21 2021-11-30 南京百思福医药科技有限公司 Photoluminescent long-acting film-forming disinfection composition and preparation method and application thereof
CN112266646B (en) * 2020-10-28 2022-07-26 广东涂强新材料有限公司 Long-acting slow-release antibacterial disinfection composition and application thereof
WO2023143490A1 (en) * 2022-01-28 2023-08-03 Nano And Advanced Materials Institute Limited Antimicrobial compositions with enhanced efficacy and prolonged performance lifetime, and preparation method thereof

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