CN110054993B - Long-life organic silicon polymer antibacterial liquid, preparation method thereof and preparation method of antibacterial coating - Google Patents
Long-life organic silicon polymer antibacterial liquid, preparation method thereof and preparation method of antibacterial coating Download PDFInfo
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- CN110054993B CN110054993B CN201910271692.6A CN201910271692A CN110054993B CN 110054993 B CN110054993 B CN 110054993B CN 201910271692 A CN201910271692 A CN 201910271692A CN 110054993 B CN110054993 B CN 110054993B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING 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
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
- C09D183/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
Abstract
The invention belongs to the field of antibacterial materials, and discloses an organic silicon polymer antibacterial liquid with a long service life, which comprises, by weight, 60-80 parts of organic silicon quaternary ammonium salt, 3-8 parts of glacial acetic acid, 5-10 parts of methyl tributyl ketoxime silane, 0.1-3 parts of an organic bismuth catalyst, and 10-20 parts of aminoalkyl alkoxy silane. The invention also discloses a preparation method of the organic silicon polymer antibacterial liquid and a preparation method of the antibacterial coating. The organic silicon polymer antibacterial mildew-proof liquid has the advantages of simple preparation process, safety, no toxicity, environmental protection, lasting and efficient antibacterial effect and long service life, meets the pursuit of people for safety, health and cleanness of living space, and accords with the consumption concept of environmental protection of people.
Description
Technical Field
The invention belongs to the field of antibacterial materials, and particularly relates to a long-life organic silicon polymer antibacterial liquid, a preparation method thereof and a preparation method of an antibacterial coating.
Background
Antibacterial coating technology has been an effective means to combat the invasion of human beings by harmful bacteria. The broad antibacterial coating is a coating with antibacterial function, which is formed by coating a binder (usually a resin or emulsion), an antibacterial agent, a plurality of auxiliary agents and the like on the surfaces of different substrates; the antibacterial agent may be organic or inorganic.
The antibacterial coatings appearing on the market at present mainly comprise two main types: (1) by UV/TiO2A photocatalytic antimicrobial coating; (2) silver ion is doped as an antibacterial coating of an antibacterial agent, but both technologies show certain defects and limitations, so that the technologies are not widely popularized and applied.
The ultraviolet light catalyzes the antibacterial coating of the titanium dioxide, and the ultraviolet light irradiation, oxygen/water vapor and the like are required to be obtained for playing a role. TiO 22The semiconductor is a semiconductor, can easily generate hydroxyl free radicals with strong oxidizing capability on the surface under the irradiation of ultraviolet light, can quickly and effectively decompose organic matters forming bacteria and organic nutrients depending on the survival of the bacteria, and can change bacterial proteins, thereby achieving the antibacterial effect. However, such coatings fail to achieve antimicrobial action away from UV light or in the dark, thus greatly limiting their indoor antimicrobial applications.
The silver-based antibacterial coating has three defects: (1) although the coating can show good antibacterial performance under the condition of no ultraviolet light, after long-time use, the coating easily causes the surface of the silver-loaded product to discolor, the color is different from light yellow to brownish black, and the color becomes darker when the concentration of the silver ions is higher, thus seriously affecting the appearance of the product. (2) The silver-doped coating slowly releases silver ions to kill bacteria, and the silver ions are completely released over time to cause failure, so that the service life of the silver-doped antibacterial coating is limited, generally about 1-3 years. (3) Silver ion is also a well-known heavy metal ion, and can cause protein denaturation after being absorbed by human body, so that the protein is inactivated and has toxicity to human body. Because of these three major drawbacks, silver-doped antimicrobial coatings have been used with some caution.
Chinese patent CN1850924A discloses a nano-silver antibacterial coating and a manufacturing method thereof, which is prepared by taking hydroxyl acrylic resin or acrylic acid synthetic emulsion as an adhesive, taking nano-silver as an antibacterial agent and then matching a small amount of auxiliary agent and water, and the obtained coating is opaque.
For another example, chinese patent CN102101959A discloses a nano antibacterial paint and its preparation method, which uses thermoplastic acrylic resin as adhesive, silver-doped nano polymer as antibacterial agent, and auxiliary agents such as defoaming agent, leveling agent, light stabilizer, etc. to make the obtained coating opaque.
For example, chinese patent CN103143067A discloses a water system antibacterial surface coating and a preparation method thereof, which is prepared by using water-based resin as an adhesive (including water-based alkyd resin, water-based polyester resin, water-based acrylic resin, water-based polyurethane resin, water-based epoxy resin and the like), using water-soluble quaternary ammonium salt as an antibacterial agent (3- (trimethoxysilyl) propyl dimethyloctadecyl ammonium chloride, dodecyl dimethyl benzyl ammonium bromide or organic silicon quaternary ammonium salt), and adding a certain amount of filler and an auxiliary agent, wherein the obtained coating is opaque.
Most of the antibacterial coatings obtained by the antibacterial coatings rely on adhesives such as resin or emulsion to ensure certain durability of the coatings; although a large amount of the antimicrobial agent is added to enhance the antimicrobial ability of the coating, in practice most of the antimicrobial agent is covered with a binder such as resin or emulsion, and only the bare outermost antimicrobial agent can exert the antimicrobial effect, and relatively, the amount of the antimicrobial agent effective in the surface of the coating is extremely small. Therefore, the antibacterial coatings obtained from these antibacterial coatings often show less than ideal antibacterial effects in practical applications. In addition, such coatings often incorporate fillers to render the coating opaque and to mask the texture of the substrate surface, thereby affecting the appearance of the substrate and limiting the application of such antimicrobial coatings. Furthermore, the antimicrobial agent on the surface of the coating is slowly dissolved out or the antimicrobial agent on the exposed part is easy to fall off due to friction in long-term use, so that the antimicrobial life of the coating is short.
Chinese patent CN107987722A discloses organosilicon bactericidal liquid, organosilicon bactericidal agent, antibacterial glass, and preparation method and application thereof, organosilicon quaternary ammonium salt is used as antibacterial agent, no resin or emulsion or other binder is present, the bactericidal rate can reach more than 99%, and the obtained coating is transparent and colorless, but the patent does not mention how long the service life of the coating is.
If the service life of the antibacterial coating is too short to meet the requirements of practical application, the antibacterial coating is an immature coating product and has no real application value. An antibacterial coating that can be applied on a large scale must have excellent function and long life, neither of which is indispensable.
In general, in numerous patents of inventions of antibacterial and mildewproof coatings, no proposal has been reported that the strong adhesion between the antibacterial agent and the base material is realized by not depending on adhesives such as resin or emulsion, the coating is colorless and transparent, the antibacterial rate reaches more than 99.9 percent, and the antibacterial life of the coating reaches more than 20 years.
Disclosure of Invention
The invention aims to provide an organosilicon polymer antibacterial liquid with a long service life.
The invention also aims to provide a preparation method of the organic silicon polymer antibacterial liquid.
It is another object of the present invention to provide a method for preparing an antibacterial coating from a silicone polymer antibacterial liquid.
In order to achieve one of the purposes, the invention adopts the following technical scheme:
the long-life organosilicon polymer antibacterial liquid comprises, by weight, 60-80 parts of organosilicon quaternary ammonium salt, 3-8 parts of glacial acetic acid, 5-10 parts of methyl tributyl ketoxime silane, 0.1-3 parts of organic bismuth catalyst and 10-20 parts of amino alkyl alkoxy silane.
Further, the organosilicon quaternary ammonium salt is selected from at least one of dimethyl octadecyl [3- (trimethoxysilyl) propyl ] ammonium chloride, dimethyl dodecyl [3- (trimethoxysilyl) propyl ] ammonium chloride, dimethyl hexadecyl [3- (trimethoxysilyl) propyl ] ammonium bromide and dimethyl octadecyl [3- (trimethoxysilyl) propyl ] ammonium fluoride.
Further, the organic bismuth catalyst is selected from at least one of organic bismuth DY-20, bismuth laurate, bismuth isooctanoate and bismuth neodecanoate.
Further, the aminoalkyl alkoxysilane is selected from 3-aminopropyltriethoxysilane and/or N- β (aminoethyl) - γ -aminopropyltrimethoxysilane.
The preparation method of the organic silicon polymer antibacterial liquid comprises the following steps:
s1, adding organosilicon quaternary ammonium salt, glacial acetic acid, methyl tributyl ketoxime silane and an organic bismuth catalyst into a reaction kettle, heating to 50-70 ℃ under the stirring condition, and reacting for 1-4 hours;
s2, cooling, and then adding aminoalkyl alkoxy silane into the system.
A preparation method of an antibacterial coating comprises the following steps:
s1, coating the organic silicon polymer antibacterial liquid on the surface of a substrate to form a uniform coating;
s2, baking the organic silicon polymer antibacterial liquid to solidify the organic silicon polymer antibacterial liquid to obtain the antibacterial coating.
Further, the coating is spray coating, dip coating or roll coating.
Further, the baking treatment temperature is 150-250 ℃, and the baking treatment time is 15-40 minutes.
Further, the thickness of the coating in the S1 is 1-5 μm.
Further, the substrate is ceramic, stainless steel, marble or glass.
The antibacterial coating can be widely applied to the following fields:
1. furniture articles: kitchen countertops, refrigerator partitions, refrigerator doors, and the like;
2. personal electrical appliance: the mobile phone comprises a mobile phone outer screen, a central touch screen, a vehicle-mounted touch screen, a robot touch screen and the like;
3. medical treatment and health: places which can be touched by human hands in hospitals, such as door handles, water taps, partition plates, medical appliances and the like;
4. kitchen bathroom: kitchen countertops, toilets, bathtubs, shower doors, etc.
Common bacteria such as escherichia coli, staphylococcus aureus, acinetobacter baumannii, klebsiella pneumoniae, pseudomonas aeruginosa, hemolytic streptococcus and the like on the surface of an object in the application field can be easily killed, the sterilization rate is up to more than 99.9%, the broad-spectrum sterilization effect is excellent, and meanwhile, the surface of the coating also has the function of not growing mould, wherein the mould mainly comprises: aspergillus niger, Penicillium funiculosum, Chaetomium globosum, Gliocladium viride special bags of willow branches, framed by bamboo, for building dykes, and the like.
The antibacterial coating can be attached to different substrates (such as fabrics, marbles, ceramics, glass, stainless steel and the like) to realize the antibacterial and mildewproof effects. According to the invention, a chemical wet method coating method is adopted, the organosilicon polymer antibacterial liquid with positive charges is uniformly coated on the surface of the base material, and then high-temperature catalytic curing is carried out, so that the organosilicon quaternary ammonium salt bactericide can chemically react with active hydroxyl of the base material to form a firm Si-O-chemical covalent bond, and thus the organosilicon antibacterial coating realizes strong adhesion on the surface of the base material, and the problems of small adhesion and easy falling-off between the traditional quaternary ammonium salt antibacterial agent and the base material are solved.
The antibacterial coating is a colorless transparent coating formed by the chemical reaction of the antibacterial liquid and active groups of the base material at high temperature, has excellent sterilization effect (the sterilization rate is up to more than 99.9%) on various bacteria, is safe, nontoxic, green and environment-friendly, and has no stimulation on human skin. The antibacterial coating has a completely transparent colorless appearance effect, so that the texture and the appearance of the base material cannot be covered, and the glossiness of the base material can be increased to a certain extent; meanwhile, the coating also has a certain anti-fingerprint effect, and the anti-fingerprint effect is not inferior to that of the common AF anti-fingerprint liquid.
The antibacterial coating really solves the problems of the existing antibacterial coatings on the market, such as: the silver antibacterial coating is easy to discolor and has short service life; UV-TiO2The coating needs to rely on ultraviolet irradiation for the antibacterial effect.
The antibacterial coating adopts the organosilicon oligomer with positive charges, and the active adhesion promoters (such as methyl tributyl ketoxime silane, aminopropyl triethoxysilane and the like) are added to carry out chemical reaction with active functional groups of various base materials (such as fabrics, marbles, ceramics, glass, stainless steel and the like) under the high-temperature catalysis to form chemical covalent bonds, so that the organosilicon polymer chain segments with the charges and the base materials are integrated into a whole, and the super-strong adhesion is shown (the appearance and the antibacterial property are not changed after boiling for 3 hours). Obviously, the antibacterial agent in the coating forms chemical covalent bonds with the base material and has good adhesion to various base materials (such as marble, ceramic, glass, stainless steel and the like), thereby ensuring that the service life of the coating can be more than 20 years. Meanwhile, the coating does not contain a binder, most of antibacterial agents can be added in the antibacterial process, and the excellent antibacterial performance is also guaranteed.
The durable and washable fabric antibacterial agent is invented by Dow Corning company in the last seventies, has the trade name of DC-5700, belongs to an organic silicon quaternary ammonium salt antibacterial agent, and is listed as a safety substance by the United states environmental protection agency.
In the antibacterial process, after the positive charges in the coating are in surface contact with negatively charged bacteria, alkyl chains are inserted into cell membranes of the bacteria, and the charge balance of the cell membranes of the bacteria is destroyed, so that the cell membranes cannot be metabolized normally, the cell membranes are broken unstably, cytoplasm flows out, and finally the bacteria die. In the antibacterial process, the organosilicon antibacterial coating only serves as a catalytic substance for destroying the cell charge balance of bacteria and does not dissolve out, so that the coating can always keep the concentration of antibacterial components in the coating to achieve a lasting and efficient antibacterial effect, and the service life of the coating can be ensured to be longer than 20 years.
The main effective component of the organosilicon polymer antibacterial liquid is organosilicon quaternary ammonium salt and oligomer thereof, and the organosilicon polymer antibacterial liquid does not contain Ag+The coating is safe and nontoxic due to the equal heavy metal ions. The antibacterial coating does not need to be irradiated by ultraviolet light, so that the universality is strong; the antibacterial coating has better wear resistance and completely meets the requirements of practical application. The antibacterial coating prepared by the method can keep long-acting sterilization effect through experimental determination, the antibacterial rate is as high as 99.9%, and the service life is as long as more than 20 years.
In addition, the antibacterial coating adopts organic bismuth with high environmental protection property as a catalyst, the organic bismuth catalyst can be cured at room temperature or heated, has strong selectivity on hydroxyl, amino and the like, and has the green safety characteristics of low cost, easy treatment, low toxicity, low radioactivity and the like, and the organic tin catalyst adopted in the prior art is not environment-friendly, toxic and causes environmental pollution.
In short, the organosilicon polymer antibacterial mildew-proof liquid disclosed by the invention is simple in preparation process, safe, nontoxic, green and environment-friendly, lasting and efficient in antibacterial effect and long in service life, meets the pursuit of people on the requirement of safety, health and cleanness of living space, and accords with the consumption concept of green and environment protection of people.
Detailed Description
The present invention will be further described with reference to the following specific examples.
Example 1
The organic silicon polymer antibacterial liquid comprises the following components: 76 parts of dimethyloctadecyl [3- (trimethoxysilyl) propyl ] ammonium chloride, 3 parts of glacial acetic acid, 7 parts of methyl tributyl ketoxime silane, 1 part of organic bismuth DY-20 and 13 parts of 3-aminopropyltriethoxysilane.
The method comprises the steps of sequentially adding dimethyl octadecyl [3- (trimethoxysilyl) propyl ] ammonium chloride, glacial acetic acid, methyl tributyl ketoxime silane and organic bismuth DY-20 into a reaction kettle, heating to 70 ℃ under the condition of stirring, reacting for 2 hours, and stopping the reaction, wherein the heating rate is 10 ℃/min. And after cooling, adding 3-aminopropyl triethoxysilane into the system to obtain the organic silicon polymer antibacterial liquid.
The organic silicon polymer antibacterial liquid is uniformly coated on the stainless steel sheet through the spraying equipment, and the antibacterial liquid layer cannot cause the problem of spraying of the appearance such as orange peel, rainbow lines, wavy lines, spots and the like.
And (3) baking the stainless steel sheet coated with the antibacterial liquid at 220 ℃ for 15min to form an antibacterial coating, thus obtaining the antibacterial stainless steel. The dry film thickness of the antimicrobial coating was about 3 μm.
Example 2
The organic silicon polymer antibacterial liquid comprises the following components: 79 parts of dimethyl octadecyl [3- (trimethoxysilyl) propyl ] ammonium chloride, 6 parts of glacial acetic acid, 5 parts of methyl tributyl ketoxime silane, 1 part of organic bismuth DY-20 and 15 parts of 3-aminopropyltriethoxysilane.
The method comprises the steps of sequentially adding dimethyl octadecyl [3- (trimethoxysilyl) propyl ] ammonium chloride, glacial acetic acid, methyl tributyl ketoxime silane and organic bismuth DY-20 into a reaction kettle, heating to 70 ℃ under the condition of stirring, reacting for 1 hour, and stopping the reaction, wherein the heating rate is 15 ℃/min. And after cooling, adding 3-aminopropyl triethoxysilane into the system to obtain the organic silicon polymer antibacterial liquid.
The organic silicon polymer antibacterial liquid is uniformly coated on the stainless steel sheet through the spraying equipment, and the antibacterial liquid layer cannot cause the problem of spraying of the appearance such as orange peel, rainbow lines, wavy lines, spots and the like.
And (3) baking the stainless steel sheet coated with the antibacterial liquid at 250 ℃ for 25min to form an antibacterial coating, thus obtaining the antibacterial stainless steel. The dry film thickness of the antimicrobial coating was about 1 μm.
Example 3
The organic silicon polymer antibacterial liquid comprises the following components: 74 parts of dimethyl octadecyl [3- (trimethoxysilyl) propyl ] ammonium chloride, 5 parts of glacial acetic acid, 7 parts of methyl tributyl ketoxime silane, 1 part of bismuth isooctanoate and 10 parts of 3-aminopropyltriethoxysilane.
Firstly, sequentially adding dimethyl octadecyl [3- (trimethoxysilyl) propyl ] ammonium chloride, glacial acetic acid, methyl tributyl ketoxime silane and bismuth isooctanoate into a reaction kettle in sequence, heating to 50 ℃ under the condition of stirring, and reacting for 4 hours, wherein the reaction can be stopped, and the heating rate is 10 ℃/min. And after cooling, adding 3-aminopropyl triethoxysilane into the system to obtain the organic silicon polymer antibacterial liquid.
The organic silicon polymer antibacterial liquid is uniformly coated on the glass sheet through the spraying equipment, and the antibacterial liquid layer can not have the problem of spraying of appearance such as orange peel, rainbow lines, wavy lines, spots and the like.
And (3) baking the glass sheet coated with the antibacterial liquid at 200 ℃ for 20min to form an antibacterial coating, thus obtaining the antibacterial glass. The dry film thickness of the antimicrobial coating was about 3 μm.
Example 4
The organic silicon polymer antibacterial liquid comprises the following components: 69 parts of dimethylhexadecyl [3- (trimethoxysilyl) propyl ] ammonium bromide, 3 parts of glacial acetic acid, 7 parts of methyl tributyl ketoxime silane, 1 part of bismuth isooctanoate and 20 parts of 3-aminopropyltriethoxysilane.
Dimethyl hexadecyl [3- (trimethoxysilyl) propyl ] ammonium bromide, glacial acetic acid, methyl tributyl ketoxime silane and bismuth isooctanoate are sequentially added into a reaction kettle, heated to 60 ℃ under the condition of stirring, reacted for 3 hours, and then the reaction is stopped, wherein the heating rate is 12 ℃/min. And after cooling, adding 3-aminopropyl triethoxysilane into the system to obtain the organic silicon polymer antibacterial liquid.
The organic silicon polymer antibacterial liquid is uniformly coated on the ceramic chip by spraying equipment, and the antibacterial liquid layer cannot have the problem of spraying of appearance such as orange peel, rainbow lines, wavy lines, spots and the like.
And (3) baking the ceramic sheet coated with the antibacterial liquid at 180 ℃ for 30min to form an antibacterial coating, so as to obtain the antibacterial ceramic. The dry film thickness of the antimicrobial coating was about 2 μm.
Example 5
The organic silicon polymer antibacterial liquid comprises the following components: 71 parts of dimethyldodecyl [3- (trimethoxysilyl) propyl ] ammonium chloride, 8 parts of glacial acetic acid, 7 parts of methyl tributyrinoxime silane, 0.5 part of bismuth isooctanoate and 10 parts of N-beta (aminoethyl) -gamma-aminopropyltrimethoxysilane.
Dimethyl dodecyl [3- (trimethoxysilyl) propyl ] ammonium chloride, glacial acetic acid, methyl tributyl ketoxime silane and bismuth isooctanoate are sequentially added into a reaction kettle, heated to 65 ℃ under the condition of stirring, reacted for 2 hours, and then the reaction is stopped, wherein the heating rate is 10 ℃/min. And after cooling, adding N-beta (aminoethyl) -gamma-aminopropyltrimethoxysilane into the system to obtain the organic silicon polymer antibacterial liquid.
The organic silicon polymer antibacterial liquid is uniformly coated on the ceramic chip by spraying equipment, and the antibacterial liquid layer cannot have the problem of spraying of appearance such as orange peel, rainbow lines, wavy lines, spots and the like.
And baking the ceramic sheet coated with the antibacterial liquid at 150 ℃ for 40min to form an antibacterial coating, thereby obtaining the antibacterial ceramic. The dry film thickness of the antimicrobial coating was about 3 μm.
Example 6
The organic silicon polymer antibacterial liquid comprises the following components: 78 parts of dimethyloctadecyl [3- (trimethoxysilyl) propyl ] ammonium fluoride, 5 parts of glacial acetic acid, 7 parts of methyl tributyl ketoxime silane, 3 parts of bismuth neodecanoate and 12 parts of 3-aminopropyltriethoxysilane.
Firstly, dimethyl octadecyl [3- (trimethoxysilyl) propyl ] ammonium fluoride, glacial acetic acid, methyl tributyl ketoxime silane and bismuth neodecanoate are sequentially added into a reaction kettle, the mixture is heated to 60 ℃ under the stirring condition, the reaction is stopped after 3 hours of reaction, and the heating rate is 15 ℃/min. And after cooling, adding 3-aminopropyl triethoxysilane into the system to obtain the organic silicon polymer antibacterial liquid.
The organic silicon polymer antibacterial liquid is uniformly coated on the marble through dip coating, and the marble coated with the antibacterial liquid is baked for 28min at 210 ℃ to form an antibacterial coating, so that the antibacterial marble is obtained. The dry film thickness of the antimicrobial coating was about 4 μm.
Example 7
The organic silicon polymer antibacterial liquid comprises the following components: 60 parts of dimethyloctadecyl [3- (trimethoxysilyl) propyl ] ammonium chloride, 4 parts of glacial acetic acid, 10 parts of methyl tributyl ketoxime silane, 0.1 part of bismuth laurate and 18 parts of 3-aminopropyltriethoxysilane.
Dimethyl octadecyl [3- (trimethoxysilyl) propyl ] ammonium chloride, glacial acetic acid, methyl tributyl ketoxime silane and bismuth laurate are sequentially added into a reaction kettle, heated to 50 ℃ under the condition of stirring, reacted for 4 hours, and then the reaction can be stopped, wherein the heating rate is 10 ℃/min. And after cooling, adding 3-aminopropyl triethoxysilane into the system to obtain the organic silicon polymer antibacterial liquid.
The organic silicon polymer antibacterial liquid is uniformly coated on the glass sheet through the spraying equipment, and the antibacterial liquid layer can not have the problem of spraying of appearance such as orange peel, rainbow lines, wavy lines, spots and the like.
And (3) baking the glass sheet coated with the antibacterial liquid at 200 ℃ for 25min to form an antibacterial coating, thus obtaining the antibacterial glass. The dry film thickness of the antimicrobial coating was about 5 μm.
Performance testing
Antibacterial effect
Escherichia coli, staphylococcus aureus and pseudomonas aeruginosa are used as experimental strains, the antibacterial performance of the bactericidal glass is tested according to the building material industry standard JC/T1054-.
TABLE 1 (E.coli)
TABLE 2 (Staphylococcus aureus)
TABLE 3 (Pseudomonas aeruginosa)
As can be seen from tables 1 to 3, the antibacterial products of examples 1 to 6 all have good antibacterial effects against Escherichia coli, Staphylococcus aureus, Pseudomonas aeruginosa, and the like. The molecular chain segment of the organosilicon quaternary ammonium salt is provided with a positive charge group, the surface of the bacteria is negatively charged, the quaternary ammonium salt is close to the bacteria due to the interaction of the charges and is inserted into the cell membrane of the bacteria to damage the integrity of the bacteria membrane, so that the bacteria can not be metabolized normally and die, and the aim of sterilization is finally achieved.
Mildew-proof effect
The antibacterial samples obtained in examples 1 to 6 were subjected to a mildew resistance test, wherein Aspergillus niger ATCC9642, Penicillium funiculosum ATCC11797, Chaetomium globosum ATCC6205, Myxomyces viridis ATCC9645 and Aureobasidium pullulans ATCC15233 were used as experimental mold species, the test time was 28 days, the test environment humidity was > 85% RH, the temperature was 28 ℃, and the test results are shown in Table 4. Wherein, the evaluation standard is as follows:
level 0: no growth
Level 1: micro-growth (the mould coverage area on the surface of the sample is less than 10%)
And 2, stage: slight growth (sample surface mould coverage area 10-30%)
And 3, level: moderate growth (the mould coverage area on the surface of the sample is 30-60%)
4, level: severe growth (mould coverage area > 60% on sample surface)
TABLE 4
| Sample name | Grade of mold growth | Degree of mold growth |
| Example 1 | Level 0 | No growth |
| Example 2 | Level 0 | No growth |
| Example 3 | Level 0 | No growth |
| Example 4 | Level 0 | No growth |
| Example 5 | Level 0 | No growth |
| Example 6 | Level 0 | No growth |
As can be seen from Table 4, the antibacterial samples obtained in examples 1 to 6 have a good mildew-proof function. The molecular chain segment of the organosilicon quaternary ammonium salt is provided with a positive charge group, enzyme in the cell wall and cells of the mould is destroyed in a non-ionized molecular form, and enzyme protein in the mould loses activity and cannot participate in catalysis, so that the proliferation of the mould is inhibited, and the mould-proof effect is achieved.
Service life
The service lives of the antibacterial products of examples 1 to 6 were measured, and the results are shown in table 5, using escherichia coli as the experimental strain, and the test indexes are MIC (minimum inhibitory concentration) and 24h sterilization rate. The service life is calculated by a high accelerated aging test and the following formula:
AF＝exp{(Ea/k)×[(1/Tu)-(1/Ts)]+(RHsn-RHun)}
in the formula:
the value of the activation energy Ea (Ea ═ 0.8eV), the recommended value in GR-1221; wherein k is Boltzmann constant, and k is 8.6 × 10-5(ii) a Tu is the normal temperature, and the value of Tu is 85 (absolute temperature); ts is the temperature in the acceleration state, and the value of Ts is 110 (absolute temperature); RHunIs the n power of normal relative humidity (n is 2 generally), and the value is 0.85; RHsnThe value is the n power (n is 2 generally) of the relative humidity in the acceleration state, and is 0.85.
The premise of this conversion is that the failure mechanism of the product is the same in both aging modes; and the basic assumption is that the product behaves in accordance with normal temperature behavior under high stress conditions.
Comparative example 1: an antimicrobial glass was prepared according to example 3, but without the addition of glacial acetic acid.
Comparative example 2: an antimicrobial glass was prepared as in example 3, but without the addition of bismuth isooctanoate.
TABLE 5
As can be seen from table 5, the sample of comparative example 1, which was made in the absence of glacial acetic acid, had the worst service life, and after 10 years had an antibacterial rate of only 25.64%; for the sample of comparative example 2 prepared in the absence of the organic bismuth catalyst, the service life is intermediate, the antibacterial rate is 80.25% after 10 years, and the antibacterial rate is only 7.69% after 20 years; the service life of the antibacterial samples obtained in the embodiments 1-6 is more than 20 years, and the antibacterial rate is generally kept above 90% after 20 years.
This is probably because the quaternary ammonium salt of organosilicon contains three active methoxyl groups, and is easily hydrolyzed into three silicon hydroxyl groups under the catalysis of acid, and the silicon hydroxyl groups are easily subjected to crosslinking polycondensation to form the oligomer/prepolymer with three-dimensional network structure. The oligomer is easy to react with active functional groups (such as hydroxyl, ester groups and the like) on the surface of a base material at high temperature (150-250 ℃) under the catalysis of organic bismuth to form covalent bonds, so that the organosilicon quaternary ammonium salt and the base material are integrated and firmly attached to the base material, and the durability and the long service life of the antibacterial coating are ensured.
It can also be seen from the comparative data in table 5 that the co-catalysis of glacial acetic acid and organobismuth is most beneficial for the lifetime of the coating, whereas glacial acetic acid alone as a catalyst has a longer lifetime than the antimicrobial coating made with organobismuth alone as a catalyst.
Patent CN107987722A uses organotin as catalyst, which on one hand causes pollution and toxicity, and on the other hand, because no acid is used for co-catalysis, chemical reaction of oligomer and substrate cannot occur, the antibacterial coating lacks durability, and the service life may not be good.
The organosilicon polymer antibacterial coating has the service life of more than 20 years, can completely meet the actual requirements under most conditions, and can become a real durable product to enter the life of people.
The above description is only an embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (9)
1. The long-life organosilicon polymer antibacterial liquid is characterized by comprising, by weight, 60-80 parts of organosilicon quaternary ammonium salt, 3-8 parts of glacial acetic acid, 5-10 parts of methyl tributyl ketoxime silane, 0.1-3 parts of an organic bismuth catalyst and 10-20 parts of aminoalkyl alkoxy silane; the organosilicon quaternary ammonium salt is selected from at least one of dimethyl octadecyl [3- (trimethoxysilyl) propyl ] ammonium chloride, dimethyl dodecyl [3- (trimethoxysilyl) propyl ] ammonium chloride, dimethyl hexadecyl [3- (trimethoxysilyl) propyl ] ammonium bromide and dimethyl octadecyl [3- (trimethoxysilyl) propyl ] ammonium fluoride.
2. The organosilicon polymer antibacterial liquid of claim 1, wherein the organic bismuth catalyst is at least one selected from organic bismuth DY-20, bismuth laurate, bismuth isooctanoate, and bismuth neodecanoate.
3. The silicone polymer antibacterial liquid of claim 1, wherein the aminoalkyl alkoxysilane is selected from 3-aminopropyltriethoxysilane and/or N- β (aminoethyl) - γ -aminopropyltrimethoxysilane.
4. The preparation method of the organosilicon polymer antibacterial liquid according to any one of claims 1 to 3, characterized by comprising the following steps:
s1, adding organosilicon quaternary ammonium salt, glacial acetic acid, methyl tributyl ketoxime silane and an organic bismuth catalyst into a reaction kettle, heating to 50-70 ℃ under the stirring condition, and reacting for 1-4 hours;
s2, cooling, and then adding aminoalkyl alkoxy silane into the system.
5. The preparation method of the antibacterial coating is characterized by comprising the following steps:
s1, coating the organosilicon polymer antibacterial liquid of any one of claims 1 to 3 on the surface of a matrix to form a uniform coating;
s2, baking the organic silicon polymer antibacterial liquid to solidify the organic silicon polymer antibacterial liquid to obtain the antibacterial coating.
6. The method of claim 5, wherein the coating is spray coating, dip coating, or roll coating.
7. The method according to claim 5, wherein the baking treatment is carried out at a temperature of 150 to 250 ℃ for 15 to 40 minutes.
8. The preparation method according to claim 5, wherein the thickness of the coating layer in S1 is 1-5 μm.
9. The method of claim 5, wherein the substrate is ceramic, stainless steel, marble, or glass.
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| CN111345295B (en) * | 2020-03-30 | 2021-10-22 | 深圳正海创新材料有限公司 | Traditional Chinese medicine oil modified active silicon antibacterial liquid and preparation method thereof, and preparation method of antibacterial coating |
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| CN113122034A (en) * | 2021-04-09 | 2021-07-16 | 柏桥生物科技有限公司 | Preparation method of antibacterial coating |
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