CN111807711A - Manufacturing process of super-hydrophilic long-life organosilicon quaternary ammonium salt antibacterial glass - Google Patents
Manufacturing process of super-hydrophilic long-life organosilicon quaternary ammonium salt antibacterial glass Download PDFInfo
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Abstract
The invention provides a manufacturing process of super-hydrophilic long-life organosilicon quaternary ammonium salt antibacterial glass. Firstly, preparing an organosilicon antibacterial liquid containing quaternary ammonium salt polyether silicone oil emulsion and quaternary ammonium salt modified mesoporous silica microspheres with the particle sizes of 20-100 nm and 100-300 nm respectively; then coating the glass surface after plasma treatment; and baking and curing to obtain the organic silicon quaternary ammonium salt antibacterial glass. According to the invention, the organic silicon antibacterial coating with the rough micro-nano structure is constructed on the surface of the glass, so that the surface of the glass is endowed with super-hydrophilicity and a self-cleaning function, dust and bacteria debris deposited on the surface are removed in time, and the antibacterial performance is improved. The mesoporous silica microspheres modified by the quaternary ammonium salt have high specific surface area, and can increase the contact area between the glass surface and bacteria, so that the antibacterial property is improved; the quaternary ammonium salinization polyether silicone oil emulsion has good film forming property, and the adhesive force and the coating property of a coating are improved.
Description
Technical Field
The invention belongs to the technical field of antibacterial glass, and particularly relates to a manufacturing process of super-hydrophilic long-life organosilicon quaternary ammonium salt antibacterial glass.
Background
In recent years, people pay more and more attention to the protection against the invasion of microorganisms so as to ensure the safety of lives and properties of the people. The antibacterial glass is a functional glass which is newly researched and developed, and adds new functions of bacteriostasis and sterilization on the basis of keeping the original functions of lighting, wind shielding and rain shielding. The increase of the function not only improves and enhances the living environment of people, but also makes the implementation of comprehensive antibacterial engineering in the industries of medical treatment, health care, household appliances and the like possible. Where glass can be used, antibacterial glass such as colored crystal glass, photovoltaic glass, hearth glass, elevator glass and the like can be used.
The antibacterial coatings appearing on the market at present mainly comprise two main types: (1) by UV/TiO2A photocatalytic antimicrobial coating; (2) the two technologies show certain defects and limitations, so that the two technologies have not been widely popularized and appliedThe application is as follows.
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.
The quaternary ammonium salt is used as an excellent non-sustained-release antibacterial agent and has the characteristics of simple preparation method, stable structure, small irritation to human bodies and broad-spectrum antibacterial property. Therefore, quaternary ammonium salts are widely studied and applied in the antibacterial field. The antibacterial mechanism of the quaternary ammonium salt is that bacteria are fully contacted with the quaternary ammonium salt through the adsorption effect of cations on the bacteria, and then the structure of the bacteria is destroyed through a long alkyl chain on the quaternary ammonium salt structure, so that the bacteria are killed. Therefore, a necessary condition for the quaternary ammonium salt to exert antibacterial action is the need for contact with germs.
Chinese patent CN107987722A discloses organosilicon bactericidal liquid, organosilicon bactericide, antibacterial glass, and preparation method and application thereof, wherein organosilicon quaternary ammonium salt is used as antibacterial agent, no resin or emulsion or other adhesive is used, the bactericidal rate can reach more than 99%, and the obtained coating is transparent and colorless. However, the patent does not mention how long the service life of the coating is, and dust and bacterial debris are easily deposited on the surface of the glass product due to the electrostatic adsorption of the silicone quaternary ammonium salt, and contact of active groups with bacteria is hindered, so that the antibacterial property is reduced.
In view of the above, the organic silicon antibacterial coating with the rough micro-nano structure is constructed on the surface of the glass, and the surface of the glass is endowed with super-hydrophilicity, so that the surface of the glass has a self-cleaning function, dust and bacteria debris deposited on the surface can be removed in time, and the antibacterial performance of the glass is improved.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a manufacturing process of super-hydrophilic long-life organosilicon quaternary ammonium salt antibacterial glass. The organic silicon antibacterial coating with the rough micro-nano structure is constructed on the surface of the glass, and the surface of the glass is endowed with super-hydrophilicity, so that the surface of the glass has a self-cleaning function, dust and bacteria debris deposited on the surface can be removed in time, and the antibacterial performance of the glass is improved.
In order to achieve the purpose, the invention adopts the following technical scheme:
a manufacturing process of super-hydrophilic long-life organosilicon quaternary ammonium salt antibacterial glass comprises the following steps:
s1, organic silicon antibacterial liquid: the preparation method comprises the following steps of preparing quaternary ammonium salinization polyether silicone oil emulsion and quaternary ammonium salt modified mesoporous silica microspheres with the particle sizes of 20-100 nm and 100-300 nm; wherein the content of the mesoporous silica microspheres modified by the quaternary ammonium salt is 10 to 30 weight percent of the quaternary ammonium salinized polyether silicone oil emulsion;
s2, glass pretreatment: carrying out plasma treatment on the cleaned glass surface to obtain surface activated glass;
s3, preparing an organic silicon antibacterial coating: coating the organic silicon antibacterial liquid obtained in the step S1 on the surface of the glass with the activated surface obtained in the step S2 to obtain an organic silicon antibacterial coating;
s4, baking and curing: and (4) baking and curing the organosilicon antibacterial coating obtained in the step (S3) to obtain the super-hydrophilic long-life organosilicon quaternary ammonium salt antibacterial glass.
Further, in the step S1, the mass ratio of the quaternary ammonium salt modified mesoporous silica microspheres with the particle diameters of 20-100 nm and 100-300 nm is 0.5: 1-2: 1.
Further, in step S1, the density of the quaternary ammonium salt functional groups on the surface of the quaternary ammonium salt modified mesoporous silica microsphere with the particle size of 20-100 nm is 0.5-3 μmol/m2(ii) a The density of quaternary ammonium salt functional groups on the surface of the quaternary ammonium salt modified mesoporous silica microsphere with the particle size of 100-300 nm is 0.25-1.5 mu mol/m2。
Further, in step S3, the thickness of the organosilicon antibacterial coating is 3-50 μm, and the density of the functional groups of the quaternary ammonium salt on the surface of the organosilicon antibacterial coating is 500-1200 μmol/m2。
Further, in step S1, the quaternary ammonium salinized polyether silicone oil emulsion includes, by weight, 20 to 40 parts of quaternary ammonium salinized polyether silicone oil, 55 to 75 parts of deionized water, and 0.5 to 1.5 parts of glacial acetic acid.
Further, the quaternary ammonium salinized polyether silicone oil is hydroxyl-terminated quaternary ammonium salinized polyether block silicone oil with the molecular weight of 12000-20000.
Further, in step S1, the preparation method of the quaternary ammonium salt modified mesoporous silica microsphere includes the following steps:
s11, uniformly mixing cetyl trimethyl ammonium bromide, sodium hydroxide, deionized water and ethanol, heating to 40-90 ℃, then dropwise adding ethyl orthosilicate and alkoxy organic silicon quaternary ammonium salt, keeping the temperature constant, reacting for 10-24 hours, centrifuging, washing and drying to obtain silicon dioxide nanoparticles;
s12, extracting the silicon dioxide nano particles obtained in the step S11 by using ethanol, and removing cetyl trimethyl ammonium bromide to obtain quaternary ammonium salt modified mesoporous silicon dioxide microspheres;
in step S11, when the concentration of sodium hydroxide is 1.8-2.5 mol/L and the temperature is 70-90 ℃, the particle size of the obtained quaternary ammonium salt modified mesoporous silica microspheres is 20-100 nm;
when the concentration of the sodium hydroxide is 1-1.8 mol/L and the temperature is 40-70 ℃, the particle size of the obtained quaternary ammonium salt modified mesoporous silica microsphere is 100-300 nm.
Further, in step S2, the atmosphere of the plasma treatment is O2、N2、NH3And Ar; the plasma treatment time is 10-20 min.
Further, in step S3, the coating includes, but is not limited to, dipping, spraying or spin coating.
Further, in step S4, the baking curing temperature is 50-280 ℃.
Advantageous effects
Compared with the prior art, the manufacturing process of the super-hydrophilic long-life organosilicon quaternary ammonium salt antibacterial glass provided by the invention has the following beneficial effects:
(1) according to the manufacturing process of the super-hydrophilic long-life organosilicon quaternary ammonium salt antibacterial glass, the quaternary ammonium salinization polyether silicone oil emulsion in the organosilicon antibacterial liquid has good film forming property and antibacterial property, and the adhesive force and the coating property of a coating on the surface of the glass can be remarkably improved. The polyether chain segment can improve the hydrophilicity of the coating, and the quaternary ammonium salt group has good antibacterial property. The mesoporous silica microspheres modified by the quaternary ammonium salt have high specific surface area, and can improve the contact area between the glass surface and bacteria, so that the antibacterial property is improved; hydroxyl on the surface of the mesoporous silica microsphere can be chemically bonded with an activated group on the surface of glass, so that the adhesive force of the coating is further improved. The method comprises the following steps of successfully constructing an organic silicon antibacterial coating with a rough micro-nano structure on the surface of glass by utilizing quaternary ammonium salt modified mesoporous silica microspheres with the particle sizes of 20-100 nm and 100-300 nm respectively, endowing the surface of the glass with super-hydrophilicity and self-cleaning functions, removing dust and bacteria debris deposited on the surface, and improving antibacterial performance.
(2) According to the manufacturing process of the super-hydrophilic long-life organosilicon quaternary ammonium salt antibacterial glass, surfaces with different rough micro-nano structures can be constructed only by regulating the proportion of the mesoporous silica microspheres modified by the quaternary ammonium salt of 20-100 nm and 100-300 nm, so that the glass with different antibacterial properties can be obtained. The mass difference of the mesoporous silica microspheres modified by the quaternary ammonium salts with two particle sizes is not too large, and the coarse micro-nano structure distribution on the surface of the coating is easy to be uneven due to the too large mass difference, so that the uniformity of the self-cleaning function of the coating is reduced. And the specific surface area and the quaternary ammonium salt functional group density of the mesoporous silica microspheres with large particle sizes are reduced, so that the addition amount is not suitable to be too large, otherwise, the antibacterial property is reduced.
(3) According to the manufacturing process of the super-hydrophilic long-life organosilicon quaternary ammonium salt antibacterial glass, the hydroxyl-terminated quaternary ammonium salinized polyether block silicone oil is preferably selected, no emulsifier is required to be additionally added, and good dispersion can be formed in an aqueous solution only by a small amount of glacial acetic acid, so that the cost is saved, and green and environment-friendly production can be realized. The terminal hydroxyl can generate chemical bonding effect with the activated group on the surface of the glass, thereby improving the adhesive force of the coating.
(4) According to the manufacturing process of the super-hydrophilic long-life organosilicon quaternary ammonium salt antibacterial glass, the antibacterial coating comprises quaternary ammonium salinized polyether silicone oil and quaternary ammonium salt modified mesoporous silica microspheres, and the long-chain polymer and the mesoporous silica microspheres can form a good synergistic antibacterial effect, so that the antibacterial and sterilization are carried out in all directions.
Drawings
FIG. 1 is a schematic view of the surface coating structure of the super-hydrophilic long-life organosilicon quaternary ammonium salt antibacterial glass.
Detailed Description
The technical solutions of the embodiments of the present invention will be described clearly and completely below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments; all other embodiments, which can be derived by a person skilled in the art from the embodiments of the present invention without any inventive step, are within the scope of the present invention.
A manufacturing process of super-hydrophilic long-life organosilicon quaternary ammonium salt antibacterial glass comprises the following steps:
s1, organic silicon antibacterial liquid: the quaternary ammonium salt polyether silicone oil emulsion is prepared by mixing quaternary ammonium salt polyether silicone oil emulsion and quaternary ammonium salt modified mesoporous silica microspheres with the particle size of 20-100 nm and 100-300 nm; wherein the content of the mesoporous silica microspheres modified by the quaternary ammonium salt is 10 to 30 weight percent of the quaternary ammonium salinized polyether silicone oil emulsion;
s2, glass pretreatment: carrying out plasma treatment on the cleaned glass surface to obtain surface activated glass;
s3, preparing an organic silicon antibacterial coating: coating the organic silicon antibacterial liquid obtained in the step S1 on the surface of the glass with the activated surface obtained in the step S2 to obtain an organic silicon antibacterial coating;
s4, baking and curing: and (4) baking and curing the organosilicon antibacterial coating obtained in the step (S3) to obtain the super-hydrophilic long-life organosilicon quaternary ammonium salt antibacterial glass.
As shown in fig. 1, by adopting the above technical scheme, the quaternary ammonium salinized polyether silicone oil emulsion in the organic silicon antibacterial liquid has good film forming property and antibacterial property, and can significantly improve the adhesion and coating property of the coating on the glass surface. The polyether chain segment can improve the hydrophilicity of the coating, and the quaternary ammonium salt group has good antibacterial property. The mesoporous silica microspheres modified by the quaternary ammonium salt have high specific surface area, and can improve the contact area between the glass surface and bacteria, so that the antibacterial property is improved; hydroxyl on the surface of the mesoporous silica microsphere can be chemically bonded with an activated group on the surface of glass, so that the adhesive force of the coating is further improved. The method comprises the following steps of successfully constructing an organic silicon antibacterial coating with a rough micro-nano structure on the surface of glass by utilizing quaternary ammonium salt modified mesoporous silica microspheres with the particle sizes of 20-100 nm and 100-300 nm respectively, endowing the surface of the glass with super-hydrophilicity and self-cleaning functions, removing dust and bacteria debris deposited on the surface, and improving antibacterial performance.
Further, in the step S1, the mass ratio of the quaternary ammonium salt modified mesoporous silica microspheres with the particle diameters of 20-100 nm and 100-300 nm is 0.5: 1-2: 1. The mass difference of the mesoporous silica microspheres modified by the quaternary ammonium salts with two particle sizes is not too large, and the coarse micro-nano structure distribution on the surface of the coating is easy to be uneven due to the too large mass difference, so that the uniformity of the self-cleaning function of the coating is reduced.
Further, in step S1, the density of the quaternary ammonium salt functional groups on the surface of the quaternary ammonium salt modified mesoporous silica microsphere with the particle size of 20-100 nm is 0.5-3 μmol/m2(ii) a The density of quaternary ammonium salt functional groups on the surface of the quaternary ammonium salt modified mesoporous silica microsphere with the particle size of 100-300 nm is 0.25-1.5 mu mol/m2. When the particle size is increased, the specific surface area is correspondingly reduced, so that the density of the quaternary ammonium salt functional groups is reduced, and the condition that the addition amount of the mesoporous silica microspheres with large particle sizes is not too large is determined, otherwise, the antibacterial property is reduced.
Further, in step S3, the thickness of the organosilicon antibacterial coating is 3-50 μm, and the density of the quaternary ammonium salt functional group on the surface of the organosilicon antibacterial coating is 500-1200 μmol/m2. The density of the quaternary ammonium salt functional group on the surface of the organosilicon antibacterial coating refers to the quaternary ammonium salt functional group contained in the coating with a certain thickness on the unit area of the glass surface. The density of the quaternary ammonium salt functional group is 500-1200 mu mol/m2In the meantime, the adsorption and deposition of the bacterial debris on the surface of the glass mainly takes the electrostatic effect, and the bacterial debris adsorbed on the surface can be quickly removed through the super-hydrophilic infiltration effect on the surface of the glass, so that the repeated durability of the antibacterial effect is realized.
Further, in step S1, the quaternary ammonium salinized polyether silicone oil emulsion includes, by weight, 20 to 40 parts of quaternary ammonium salinized polyether silicone oil, 55 to 75 parts of deionized water, and 0.5 to 1.5 parts of glacial acetic acid. The quaternary ammonium salinization polyether silicone oil can form good dispersion in aqueous solution only by a small amount of glacial acetic acid without adding an emulsifier, so that the cost is saved, and green and environment-friendly production can be realized.
Further, the quaternary ammonium salinized polyether silicone oil is hydroxyl-terminated quaternary ammonium salinized polyether block silicone oil with the molecular weight of 12000-20000. The hydroxyl-terminated quaternary ammonium salinized polyether block silicone oil is adopted, and the hydroxyl-terminated quaternary ammonium salinized polyether block silicone oil can generate chemical bonding effect with an activated group on the surface of glass, so that the adhesive force of a coating is improved.
Further, in step S1, the preparation method of the quaternary ammonium salt modified mesoporous silica microsphere includes the following steps:
s111, uniformly mixing cetyl trimethyl ammonium bromide, sodium hydroxide, deionized water and ethanol, heating to 40-90 ℃, then dropwise adding ethyl orthosilicate and alkoxy organosilicon quaternary ammonium salt, keeping the temperature constant, reacting for 10-24 hours, centrifuging, washing and drying to obtain silicon dioxide nanoparticles;
and S112, extracting the silica nanoparticles obtained in the step S11 by using ethanol, and removing cetyl trimethyl ammonium bromide to obtain the quaternary ammonium salt modified mesoporous silica microspheres.
In step S11, when the concentration of sodium hydroxide is 1.8-2.5 mol/L and the temperature is 70-90 ℃, the particle size of the obtained quaternary ammonium salt modified mesoporous silica microspheres is 20-100 nm;
when the concentration of the sodium hydroxide is 1-1.8 mol/L and the temperature is 40-70 ℃, the particle size of the obtained quaternary ammonium salt modified mesoporous silica microsphere is 100-300 nm. The concentration of sodium hydroxide and the reaction temperature are increased, the hydrolysis rate of the tetraethoxysilane is accelerated, the number of formed crystal nuclei is increased, and the particle size is reduced. Conversely, the particle size increases.
Further, in step S2, the atmosphere of the plasma treatment is O2、N2、NH3And Ar; the plasma treatment time is 10-20 min. After the glass is subjected to plasma treatment, active groups such as hydroxyl, amino, carboxyl and the like are formed on the surface of the glass, and the active groups are easy to be chemically bonded with the active groups in the organosilicon antibacterial liquid, so that the adhesive force of the coating is improved.
Further, in step S3, the coating includes, but is not limited to, dipping, spraying or spin coating.
Further, in step S4, the baking curing temperature is 50-280 ℃. When the glass is baked at high temperature, the organosilicon antibacterial liquid is solidified, and an antibacterial coating with excellent adhesive force and coating property is formed on the surface of the glass. The quaternary ammonium salinized polyether silicone oil and the quaternary ammonium salt modified mesoporous silicon dioxide microspheres in the coating have good heat-resistant stability, so that thermal degradation damage cannot occur during baking.
Example 1
A manufacturing process of super-hydrophilic long-life organosilicon quaternary ammonium salt antibacterial glass comprises the following steps:
s1, organic silicon antibacterial liquid: adding the quaternary ammonium salt modified mesoporous silica microspheres with the particle sizes of 20-40 nm and 100-120 nm into the quaternary ammonium salinized polyether silicone oil emulsion, and uniformly stirring to obtain an organic silicon antibacterial liquid; wherein the content of the quaternary ammonium salt modified mesoporous silica microspheres is 20 wt% of the quaternary ammonium salinized polyether silicone oil emulsion, the mass ratio of the quaternary ammonium salt modified mesoporous silica microspheres with the particle diameters of 20-100 nm and 100-300 nm is 1:1, and the density of the quaternary ammonium salt functional groups is 2 mu mol/m2And 1. mu. mol/m2。
The quaternary ammonium salinized polyether silicone oil emulsion comprises 30 parts by weight of hydroxyl-terminated quaternary ammonium salinized polyether block silicone oil with the molecular weight of 15000, 69.2 parts by weight of deionized water and 0.8 part by weight of glacial acetic acid.
The preparation method of the quaternary ammonium salt modified mesoporous silica microsphere comprises the following steps:
s11, uniformly mixing cetyl trimethyl ammonium bromide, sodium hydroxide, deionized water and ethanol, heating to 40-90 ℃, then dropwise adding ethyl orthosilicate and alkoxy organic silicon quaternary ammonium salt, keeping the temperature constant, reacting for 10-24 hours, centrifuging, washing and drying to obtain silicon dioxide nanoparticles;
s12, extracting the silicon dioxide nano particles obtained in the step S11 by using ethanol, and removing cetyl trimethyl ammonium bromide to obtain quaternary ammonium salt modified mesoporous silicon dioxide microspheres;
in step S11, when the concentration of sodium hydroxide is 1.8-2.5 mol/L and the temperature is 70-90 ℃, the particle size of the obtained quaternary ammonium salt modified mesoporous silica microspheres is 20-40 nm;
when the concentration of the sodium hydroxide is 1-1.8 mol/L and the temperature is 40-70 ℃, the particle size of the obtained quaternary ammonium salt modified mesoporous silica microsphere is 100-120 nm.
S2, glass pretreatment: plasma treatment of the cleaned glass surfaceObtaining glass with activated surface; the atmosphere of the plasma treatment is equal volume ratio of O2And N2(ii) a The plasma treatment time was 15 min.
S3, preparing an organic silicon antibacterial coating: uniformly coating the organic silicon antibacterial liquid obtained in the step S1 on the surface of the glass with the activated surface obtained in the step S2 by using spraying equipment to obtain an organic silicon antibacterial coating;
s4, baking and curing: and (4) baking and curing the organosilicon antibacterial coating obtained in the step (S3) at 250 ℃ to obtain the super-hydrophilic long-life organosilicon quaternary ammonium salt antibacterial glass with the coating thickness of 20 mu m. The test shows that the functional group density of the quaternary ammonium salt on the surface of the organosilicon antibacterial coating is 800 mu mol/m2。
Example 2
Compared with the embodiment 1, the difference of the manufacturing process of the super-hydrophilic long-life organosilicon quaternary ammonium salt antibacterial glass is that in step S1, the quaternary ammonium salinized polyether silicone oil emulsion comprises 30 parts by weight of quaternary ammonium salinized polyether block silicone oil with the molecular weight of 18000, 69.2 parts by weight of deionized water and 0.8 part by weight of glacial acetic acid. The rest is substantially the same as that of embodiment 1, and will not be described herein.
Examples 3 to 8
The manufacturing processes of the superhydrophilic long-life organosilicon quaternary ammonium salt antibacterial glass provided in embodiments 3 to 8 are different from those of embodiment 1 in that the particle size of the quaternary ammonium salt modified mesoporous silica microspheres and the mass ratio of the small particle size to the large particle size are shown in table 1. The rest is substantially the same as that of embodiment 1, and will not be described herein.
TABLE 1 particle size and mass ratio of small particle size to large particle size of quaternary ammonium salt-modified mesoporous silica microspheres
| Examples | Small particle size (nm) | Large particle size (nm) | Mass ratio of |
| Example 3 | 20～40 | 100～120 | 0.5:1 |
| Example 4 | 20～40 | 100～120 | 1:2 |
| Example 5 | 40～60 | 100～120 | 1:1 |
| Example 6 | 80～100 | 100～120 | 1:1 |
| Example 7 | 20～40 | 130～150 | 1:1 |
| Example 8 | 20～40 | 160～180 | 1:1 |
Comparative example 1
Compared with the embodiment 1, the manufacturing process of the super-hydrophilic long-life organosilicon quaternary ammonium salt antibacterial glass is different in that in the step S1, only the mesoporous silica microspheres modified by the quaternary ammonium salt with the particle size of 20-40 nm are included. The rest is substantially the same as that of embodiment 1, and will not be described herein.
Comparative example 2
Compared with the embodiment 1, the manufacturing process of the super-hydrophilic long-life organosilicon quaternary ammonium salt antibacterial glass is characterized in that in the step S1, only the mesoporous silica microspheres modified by the quaternary ammonium salt with the particle size of 100-120 nm are included. The rest is substantially the same as that of embodiment 1, and will not be described herein.
Comparative example 3
Compared with the embodiment 1, the difference of the manufacturing process of the super-hydrophilic long-life organosilicon quaternary ammonium salt antibacterial glass is that in the step S1, mesoporous silica microspheres modified by quaternary ammonium salt are replaced by mesoporous silica microspheres, namely, in the step S11, alkoxy organosilicon quaternary ammonium salt is not added. The rest is substantially the same as that of embodiment 1, and will not be described herein.
Comparative example 4
Compared with the embodiment 1, the difference of the manufacturing process of the super-hydrophilic long-life organosilicon quaternary ammonium salt antibacterial glass is that in the step S1, the mesoporous silica microspheres modified by quaternary ammonium salt are not added. The rest is substantially the same as that of embodiment 1, and will not be described herein.
Comparative example 5
Compared with the manufacturing process of the super-hydrophilic long-life organosilicon quaternary ammonium salt antibacterial glass in the embodiment 1, the manufacturing process of the super-hydrophilic long-life organosilicon quaternary ammonium salt antibacterial glass is different in that the glass is not subjected to plasma treatment in the step S2. The rest is substantially the same as that of embodiment 1, and will not be described herein.
The super-hydrophilic long-life organosilicon quaternary ammonium salt antibacterial glass obtained in the examples 1-8 and the comparative examples 1-5 is subjected to antibacterial performance and contact angle tests. The antibacterial performance of the bactericidal glass is tested according to the standard GB/T21866-2008, the 24-hour bactericidal rate of the glass is tested, the antibacterial performance is evaluated according to the antibacterial rate obtained by calculation, and the results are shown in Table 2. The strain is Escherichia coli and Staphylococcus aureus.
TABLE 2 contact angles and antibacterial properties of examples 1 to 8 and comparative examples 1 to 5
As can be seen from Table 2, the contact angle of the surface of the super-hydrophilic long-life organosilicon quaternary ammonium salt antibacterial glass prepared by the invention is less than 10 degrees, and the contact angle is obviously increased when only one quaternary ammonium salt modified mesoporous silica microsphere with a particle size is used in comparative examples 1 and 2 and when no mesoporous silica microsphere is added. The invention successfully constructs a rough micro-nano structure, and improves the hydrophilicity and self-cleaning performance of the rough micro-nano structure. The antibacterial coating comprises quaternary ammonium salinized polyether silicone oil and quaternary ammonium salt modified mesoporous silica microspheres, and the long-chain polymer and the mesoporous silica microspheres can form a good synergistic antibacterial effect, so that the antibacterial and sterilization can be carried out in all directions.
The super-hydrophilic long-life organosilicon quaternary ammonium salt antibacterial glass prepared in the example 1 is subjected to an antibacterial durability test by the following method:
1. wear resistance: grind 1000 times with 750 g, wool pad. All test results were carried out to test the bactericidal effect of the coating after the test. The sterilization rate is less than 90 percent, the sterilization rate is unqualified, the sterilization rate is higher than 90 percent, the sterilization rate is qualified, and the sterilization rate is preferably higher than 95 percent.
2. Acid resistance: 2 products are taken and tested under the condition of 1MHC1 for 24 hours, and the coating surface is observed from the front surface without the phenomena of swelling, peeling and falling off. The sterilization rate is still more than 99.99 percent after the test.
3. Alkali resistance: 2 pieces of the product are tested for 24 hours under the condition that the PH value is 10, and the coating surface is observed from the front surface to have no phenomena of swelling, peeling and falling off.
4. Solvent resistance: 2 pieces of the product, 75% alcohol, were taken for 24 hours for experiments, and the coating surface was observed from the front surface to have no damage, discoloration, dissolution, and peeling.
5. Boiling water resistance: 2 samples are taken for 1 hour for experiment, and the coating surface is observed from the front side without peeling and cracking.
6. Moisture and heat resistance: 2 samples (58 ℃ and 95% humidity samples for 500 hours) are taken for experiment, and the phenomena of swelling, discoloration, peeling and falling of the coating surface are observed from the front.
7. Moisture and freezing resistance: 2 samples (20 ℃ below zero/80 ℃ for one week) are taken for experiment, and the coating surface is observed from the front side without peeling, cracking and falling-off phenomena.
8. Ultraviolet resistance: 2 samples (15 kWH/m)2200 hours), and the coating surface is observed from the front surface without fading, peeling and falling off. The test results are shown in table 3.
TABLE 3 antimicrobial durability of example 1 and comparative examples 1-5
The super-hydrophilic long-life organosilicon quaternary ammonium salt antibacterial glass prepared in the example 1 is subjected to durability and cleaning performance tests, and the test results are shown in the table 4.
Table 4 durability and cleaning performance of antimicrobial glass prepared in example 1
As can be seen from table 4, the antibacterial glass coating prepared by the present invention has good durability and easy-to-clean performance.
In conclusion, the invention successfully constructs the organic silicon antibacterial coating with the rough micro-nano structure on the glass surface by using the quaternary ammonium salt modified mesoporous silica microspheres with the particle diameters of 20-100 nm and 100-300 nm respectively, endows the glass surface with super-hydrophilicity and self-cleaning functions, removes dust and bacteria debris deposited on the surface and improves the antibacterial performance. The quaternary ammonium salinization polyether silicone oil emulsion in the organic silicon antibacterial liquid has good film forming property and antibacterial property, and can remarkably improve the adhesive force and the coating property of a coating on the surface of glass. The polyether chain segment can improve the hydrophilicity of the coating, and the quaternary ammonium salt group has good antibacterial property. The mesoporous silica microspheres modified by the quaternary ammonium salt have high specific surface area, and can improve the contact area between the glass surface and bacteria, so that the antibacterial property is improved; hydroxyl on the surface of the mesoporous silica microsphere can be chemically bonded with an activated group on the surface of glass, so that the adhesive force of the coating is further improved.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (10)
1. A manufacturing process of super-hydrophilic long-life organosilicon quaternary ammonium salt antibacterial glass is characterized by comprising the following steps:
s1, organic silicon antibacterial liquid: the preparation method comprises the following steps of preparing quaternary ammonium salinization polyether silicone oil emulsion and quaternary ammonium salt modified mesoporous silica microspheres with the particle sizes of 20-100 nm and 100-300 nm; wherein the content of the mesoporous silica microspheres modified by the quaternary ammonium salt is 10 to 30 weight percent of the quaternary ammonium salinized polyether silicone oil emulsion;
s2, glass pretreatment: carrying out plasma treatment on the cleaned glass surface to obtain surface activated glass;
s3, preparing an organic silicon antibacterial coating: coating the organic silicon antibacterial liquid obtained in the step S1 on the surface of the glass with the activated surface obtained in the step S2 to obtain an organic silicon antibacterial coating;
s4, baking and curing: and (4) baking and curing the organosilicon antibacterial coating obtained in the step (S3) to obtain the super-hydrophilic long-life organosilicon quaternary ammonium salt antibacterial glass.
2. The manufacturing process of the super-hydrophilic long-life organosilicon quaternary ammonium salt antibacterial glass as claimed in claim 1, wherein in step S1, the mass ratio of the quaternary ammonium salt modified mesoporous silica microspheres with the particle diameters of 20-100 nm and 100-300 nm is 0.5: 1-2: 1.
3. The manufacturing process of the super-hydrophilic long-life organosilicon quaternary ammonium salt antibacterial glass as claimed in claim 1, wherein in step S1, the density of quaternary ammonium salt functional groups on the surface of the quaternary ammonium salt modified mesoporous silica microsphere with the particle size of 20-100 nm is 0.5-3 μmol/m2(ii) a The density of quaternary ammonium salt functional groups on the surface of the quaternary ammonium salt modified mesoporous silica microsphere with the particle size of 100-300 nm is 0.25-1.5 mu mol/m2。
4. The manufacturing process of the super-hydrophilic long-life antibacterial glass containing organosilicon quaternary ammonium salt as claimed in claim 1, wherein in step S3, the thickness of the organosilicon antibacterial coating is 3-50 μm, and the functional group density of the quaternary ammonium salt on the surface of the organosilicon antibacterial coating is 500-1200 μmol/m2。
5. The manufacturing process of the super-hydrophilic long-life organosilicon quaternary ammonium salt antibacterial glass as claimed in claim 1, wherein in step S1, the quaternary ammonium salinized polyether silicone oil emulsion comprises 20-40 parts by weight of quaternary ammonium salinized polyether silicone oil, 55-75 parts by weight of deionized water and 0.5-1.5 parts by weight of glacial acetic acid.
6. The manufacturing process of the super-hydrophilic long-life organosilicon quaternary ammonium salt antibacterial glass according to claim 5, characterized in that the quaternary ammonium salinized polyether silicone oil is a hydroxyl-terminated quaternary ammonium salinized polyether block silicone oil with a molecular weight of 12000-20000.
7. The manufacturing process of the super-hydrophilic long-life organosilicon quaternary ammonium salt antibacterial glass as claimed in claim 1, wherein in step S1, the preparation method of the quaternary ammonium salt modified mesoporous silica microsphere comprises the following steps:
s11, uniformly mixing cetyl trimethyl ammonium bromide, sodium hydroxide, deionized water and ethanol, heating to 40-90 ℃, then dropwise adding ethyl orthosilicate and alkoxy organic silicon quaternary ammonium salt, keeping the temperature constant, reacting for 10-24 hours, centrifuging, washing and drying to obtain silicon dioxide nanoparticles;
s12, extracting the silicon dioxide nano particles obtained in the step S11 by using ethanol, and removing cetyl trimethyl ammonium bromide to obtain quaternary ammonium salt modified mesoporous silicon dioxide microspheres;
in step S11, when the concentration of sodium hydroxide is 1.8-2.5 mol/L and the temperature is 70-90 ℃, the particle size of the obtained quaternary ammonium salt modified mesoporous silica microspheres is 20-100 nm;
when the concentration of the sodium hydroxide is 1-1.8 mol/L and the temperature is 40-70 ℃, the particle size of the obtained quaternary ammonium salt modified mesoporous silica microsphere is 100-300 nm.
8. The manufacturing process of the super-hydrophilic long-life organosilicon quaternary ammonium salt antibacterial glass according to claim 1, wherein in step S2, the atmosphere of the plasma treatment is O2、N2、NH3And Ar; the plasma treatment time is 10-20 min.
9. The manufacturing process of the super-hydrophilic long-life organosilicon quaternary ammonium salt antibacterial glass according to claim 1, wherein in step S3, the coating includes but is not limited to dipping, spraying or spin coating.
10. The manufacturing process of the super-hydrophilic long-life organosilicon quaternary ammonium salt antibacterial glass according to claim 1, wherein in step S4, the baking and curing temperature is 50-280 ℃.
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