CN115895367A - Preparation method of organic-inorganic hybrid super-hydrophilic emulsion - Google Patents
Preparation method of organic-inorganic hybrid super-hydrophilic emulsion Download PDFInfo
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- 239000000839 emulsion Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 16
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000243 solution Substances 0.000 claims abstract description 11
- 239000007864 aqueous solution Substances 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims abstract description 7
- 239000011259 mixed solution Substances 0.000 claims abstract description 6
- 239000003945 anionic surfactant Substances 0.000 claims abstract description 5
- 230000002378 acidificating effect Effects 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 239000002245 particle Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- 239000002105 nanoparticle Substances 0.000 claims description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- 125000003342 alkenyl group Chemical group 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- 238000000576 coating method Methods 0.000 description 152
- 239000011248 coating agent Substances 0.000 description 147
- 238000009835 boiling Methods 0.000 description 24
- 238000005299 abrasion Methods 0.000 description 16
- 239000000758 substrate Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- 239000011521 glass Substances 0.000 description 12
- 230000008859 change Effects 0.000 description 10
- 239000011247 coating layer Substances 0.000 description 10
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- 239000003513 alkali Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 238000002834 transmittance Methods 0.000 description 8
- 238000005507 spraying Methods 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 6
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- 238000012876 topography Methods 0.000 description 5
- 229910004298 SiO 2 Inorganic materials 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
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- 238000002791 soaking Methods 0.000 description 3
- 239000012780 transparent material Substances 0.000 description 3
- 229920002125 Sokalan® Polymers 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
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- 239000007921 spray Substances 0.000 description 2
- 239000005328 architectural glass Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
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- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
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- 230000007423 decrease Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000005660 hydrophilic surface Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 239000002103 nanocoating Substances 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
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Abstract
The invention discloses a preparation method of organic-inorganic hybrid super-hydrophilic emulsion, which comprises the following steps: (1) Adding 2-5 parts by mass of acidic silica sol into 100-200 parts by mass of water, and adding hydrochloric acid into the water; (2) Adding 2-10 parts by mass of polyacrylic resin emulsion into the solution obtained in the step (1), and stirring to obtain a mixed solution; (3) And (3) adding 0.1-2 parts by mass of tetraethyl orthosilicate aqueous solution into the mixed solution obtained in the step (2), reacting in a water bath at 50-60 ℃, adding 1-2 parts by mass of anionic surfactant after reaction, and uniformly mixing to obtain the organic-inorganic hybrid super-hydrophilic emulsion.
Description
Technical Field
The invention relates to a preparation method of organic-inorganic hybrid super-hydrophilic emulsion.
Background
Transparent glass and polymer materials have excellent optical properties and are widely used in daily life. When the materials are actually used, temperature difference changes are generated due to environmental changes, water vapor in the air is easily condensed into water drops on the surfaces of the materials, fog is generated, and the transparency and the visibility of the materials are reduced sharply. For example, swimming goggles, glasses, bathroom goggles, greenhouses, solar panels, etc. used in daily life often affect the use of transparent materials due to the phenomenon of fogging and frosting on the surface, so the antifogging property of the transparent materials is very important. Aiming at the problem, the prior art is to attach an antifogging coating on the surface of a transparent material, the hydrophilicity of the surface of the material is changed through the antifogging coating, and the hydrophilic surface can enable water to spread into a uniform water film on the surface of the material, so that the refraction and reflection of light are not generated, and the light transmittance of the material is kept.
At present, based on SiO 2 The antifogging coating of nano particles is a very effective hydrophilic antifogging coating, but an important problem existing in the application of the antifogging coating on a transparent glass substrate is that the hydrophilic durability and the optical performance of the coating are difficult to meet the requirements at the same time, and on one hand, the thickness of an inorganic nano coating is often determined by the thickness of stacked SiO 2 Excessive SiO determined by the nanoparticles 2 The random accumulation of the nanoparticles can cause the optical performance of the coating to be reduced sharply, such as excessive haze or structural color, but the too low thickness of the coating can make the hydrophilic durability of the coating difficult to meet the requirements of practical application.
Disclosure of Invention
The invention aims to: the invention aims to provide a preparation method of an organic-inorganic hybrid super-hydrophilic coating, and the super-hydrophilic coating obtained by the method has good hydrophilic durability while maintaining good light transmission.
The technical scheme is as follows: the preparation method of the organic-inorganic hybrid super-hydrophilic coating comprises the following steps:
(1) Adding 2-5 parts by mass of acidic silica sol into 100-200 parts by mass of water, adding hydrochloric acid into the water, and adjusting the pH value of the solution to 4-5;
(2) Adding 2-10 parts by mass of polyacrylic resin emulsion into the solution obtained in the step (1), and stirring to obtain a mixed solution;
(3) And (3) adding 0.1-2 parts by mass of tetraethyl orthosilicate aqueous solution into the mixed solution obtained in the step (2), reacting in a water bath at 50-60 ℃, adding 1-2 parts by mass of anionic surfactant after reaction, and uniformly mixing to obtain the organic-inorganic hybrid super-hydrophilic coating.
Wherein, in the step (1), the silica sol is O-type silica sol. Micelles in the acidic silica sol can form a two-dimensional or three-dimensional network structure under the catalytic action of hydrochloric acid, and can generate strong adsorbability with tetraethoxysilane and polyacrylic acid in a system, so that the strength of the coating and the adhesion with a substrate are enhanced.
Wherein, in the step (1), the particle diameter of the silicon dioxide nano particles in the silica sol is 3-10 nm, and the solid content is not less than 20%.
Wherein, in the step (2), the mass concentration of the polyacrylic resin in the polyacrylic resin emulsion is not higher than 3.0%.
In the step (3), the mass concentration of tetraethyl orthosilicate in the tetraethyl orthosilicate aqueous solution is not less than 2.0%.
Wherein, in the step (3), the anionic surfactant is sodium alkenyl sulfonate.
The application process of the super-hydrophilic coating comprises the following steps: and (3) forming a film on the surface of the substrate by spraying, dipping, lifting, brushing or roller coating the super-hydrophilic coating, and curing for 24 hours at normal temperature to obtain the completely cured transparent super-hydrophilic antifogging coating. The substrate comprises automotive glass, architectural glass or optical lens glass.
Because the particle size of the nano particles in the inorganic emulsion is small (3-10 nm), the specific surface area is large, the surface energy is large, the nano particles are in an energy unstable state, the particles tend to be aggregated together and generate agglomeration, polyacrylic resin is introduced into the inorganic emulsion and is stirred at high speed, emulsion components are fully dispersed under the action of external shearing force and impact force, and the polyacrylic resin is adsorbed on the surfaces of the nano particles to form a protective layer consisting of organic branched chains, so that the agglomeration of the nano particles in a coating is avoided, the long-term stability of the emulsion is ensured, and the prepared coating has good light transmittance (lambda =550nm, more than 90%); the addition of the polyacrylic resin in the inorganic emulsion increases the contact area between the coating and the base material, meanwhile, the-COOH rich in the resin and-OH on the surface of the glass substrate are subjected to chemical crosslinking, so that the bonding strength between the coating and the substrate is further improved, the adhesive force of the coating reaches 4.21MPa, the peeling condition of the coating after long-term abrasion and boiling is effectively relieved, and the abrasion resistance and boiling resistance of the coating are enhanced.
Has the advantages that: compared with the prior art, the invention has the following remarkable effects: compared with the existing inorganic coating, the coating formed by the organic-inorganic hybrid super-hydrophilic coating has more durable hydrophilic performance and equivalent light transmittance under the same thickness, and has good bonding strength with the substrate, so that the coating still has super-hydrophilic performance after being rubbed and soaked in water (after a Taber abrasion tester wears 300 turns under 250g load and boils for 60 minutes), the contact angle of the coating is about 6 degrees after boiling for 60 minutes, and the contact angle of the coating after wearing 300 turns can also be maintained at about 6 degrees; the super-hydrophilic coating is applied to automobile glass, building glass or optical lens glass, does not affect the hardness, transparency and the like of the glass, and has the capability of easy cleaning and antifogging.
Drawings
FIG. 1 is a flow chart of the coating and the process for the final coating of the present invention;
FIG. 2 is a surface topography of a coating formed from the example 1 coating and a coating formed from the comparative example 1 coating;
FIG. 3 is a comparison of the wear resistance of the coating formed from the coating of example 1 and the coating formed from the coating of comparative example 1;
FIG. 4 is a graph showing the effect of polyacrylic resin content on the appearance and particle size of the coating; wherein (a) is a light transmittance demonstration of example 1 and comparative example 2; (b) The relationship between the particle size of the particles in the coating and the content of the polyacrylic resin;
FIG. 5 is a surface topography at a single scratch and wear interface at different magnifications; wherein, (a) and (b) are abraded for 60 revolutions; (c) and (d) abrasion is 120 turns; (e) and (f) are abraded for 180 revolutions; (g) abrasion 240 turns; (i), (j) abrasion 300 turns;
FIG. 6 is the relationship between S element content and wettability of the coating surface and the abrasion rotation number; wherein (a) is the relation between the S element content of the coating surface and the abrasion revolution; (b) The relationship between the wettability and the actual antifogging effect of the coating and the abrasion revolution is shown;
FIG. 7 is a graph showing the change in surface morphology during boiling of a coating at different rates; wherein (a) and (b) are boiled for 10 minutes; (c) and (d) are boiled for 20 minutes; (e) After boiling for 30 minutes, (g) and (h) after boiling for 40 minutes; (i), (j) after boiling for 50 minutes;
FIG. 8 is the relationship between S element content and wettability of the coating surface and boiling time; wherein, (a) is the relation between the S element content on the surface of the coating and the boiling time, and (b) is the relation between the wettability and the actual antifogging effect of the coating and the boiling time;
FIG. 9 is the change of the initial surface topography of the coating with TEOS content under different multiplying powers; wherein (a) and (b) are TEOS-free; (c), (d) 0.5wt.% TEOS; (e) (f) 1wt.% TEOS, (g) 1.5wt.% TEOS; (i), (j) 2.0wt.% TEOS;
FIG. 10 shows the change of the surface topography of the coating with TEOS content after the coating is worn for 300 turns under different multiplying factors; wherein, (a) and (b) are TEOS-free; (c), (d) 0.5wt.% TEOS; (e) (f) 1wt.% TEOS, (g) 1.5wt.% TEOS; (i), (j) 2.0wt.% TEOS;
FIG. 11 is a graph of TEOS content as a function of coating durability;
FIG. 12 is the change of the surface topography of the coating with TEOS content after the coating is boiled for 1h under different multiplying factors; wherein, (a) and (b) are TEOS-free; (c), (d) 0.5wt.% TEOS; (e) (f) 1wt.% TEOS, (g) 1.5wt.% TEOS; (i), (j) 2.0wt.% TEOS;
FIG. 13 shows the acid and alkali resistance of the coating; wherein (a) is the change of WCA on the surface of the coating soaked in acid-base solution along with the soaking time; (b) The appearance photos of the inorganic coating and the hybrid coating after alkali resistance test;
FIG. 14 is a graph showing the variation of WCA on the surface of the coating as a function of time; wherein, the insets are appearance photos after 50 days of aging resistance test;
FIG. 15 is a graph of WCA as a function of ambient temperature for the coated surface.
Detailed Description
The technical scheme of the invention is further explained by combining the attached drawings.
Example 1
The preparation method of the organic-inorganic hybrid super-hydrophilic coating specifically comprises the following steps: adding 2.5g of O-type silica sol (silica sol with the pH of 2-4, the particle size of 3-10 nm and the solid content of 20%) into 100g of deionized water, dropwise adding 300 mu L of hydrochloric acid (the mass fraction of the hydrochloric acid is 38%), stirring uniformly at room temperature, adding 2g of polyacrylic resin emulsion (the mass concentration of the polyacrylic resin in the polyacrylic resin emulsion is 3.0%) into the solution, and continuously stirring uniformly; then adding 2g of tetraethyl orthosilicate aqueous solution (the mass concentration of tetraethyl orthosilicate in the tetraethyl orthosilicate aqueous solution is 2.0%), stirring for 12 hours in a water bath environment at 50 ℃, adding 1.6g of sodium alkenyl sulfonate, and stirring uniformly to obtain the organic-inorganic hybrid super-hydrophilic coating.
The coating prepared in example 1 is sprayed on the glass sheet at room temperature, the distance between the spray guns is kept at 20-30 cm, the air output of the spray guns is reduced during spraying to achieve the effect of dry spraying, the substrate is sprayed to be wet through wet spraying after being sprayed for several times, the spraying is finished, the uniformity of the coating on the surface of the substrate is kept as much as possible during spraying, and the phenomena of non-uniformity such as liquid accumulation, sagging and the like are avoided (the spraying amount is 1 m) 2 650 g) of the coating, curing for 24 hours at normal temperature to obtain the antifogging coating, wherein the thickness of the antifogging coating is 3.4 mu m, and the light transmittance of the coating is 90.0 percent.
Comparative example 1
Comparative example 1 was prepared identically to example 1, except that: adding 2g of polyurethane resin emulsion (the mass concentration of polyurethane resin in the polyurethane resin emulsion is 3.0%), and the surface of the finally obtained coating has an obvious porous structure, as shown in fig. 2, (a) is that the surface of the coating of comparative example 1 has an obvious porous structure, and (b) and (c) are higher multiplying power, a large amount of spherical nanoparticles can be observed to be exposed on the surface of the coating through the holes; (d) And (e) and (f) are the surfaces of the coatings of the embodiment 1, compared with the surfaces of the coatings of the embodiment 1, the coatings are more uniform and compact, and no obvious naked spherical nano particles are seen.
After 240 revolutions of abrasion of the Taber abrader at the same coating thickness, the PU-SiO 2 The water contact angle of the coating is close to 15 degrees, the super-hydrophilicity is lost, and the super-hydrophilicity antifogging effect is obviously reduced; PAA-SiO under the same test period 2 The water contact angle of the coating is only about 6 degrees, and the good super-hydrophilic antifogging effect is still kept. The results show that although the introduction of PU and PAA can effectively improve the adhesion between the coating and the substrate, the PAA-SiO 2 Compared with PU-SiO, the surface of the coating is 2 The surface of the coating is more uniform and compact, so that the strength of the coating is relatively higher, and the coating finally has more excellent wear resistance. As can be seen from fig. 3, the abrasion resistance of the example 1 coating is significantly better than that of the comparative example 1 coating.
Comparative example 2
Comparative example 2 was prepared identically to example 1, except that: the mass concentration of the polyacrylic resin in the polyacrylic resin emulsion was adjusted to 1wt.%, 2wt.%, 4wt.%, and 5wt.%, respectively. The particle size of the nanoparticles in the coating increases with the content of the polyacrylic resin, as shown in fig. 4, the particle size of the nanoparticles in the coating with the mass concentration of the polyacrylic resin of 1wt.% is 48nm, while the particle size of the particles in the coating with the mass concentration of the polyacrylic resin of 5wt.% reaches 366nm, and the light transmittance of the coating is obviously reduced. The increase of the particle size can increase the roughness of the surface of the coating so as to enhance the scattering effect on light on one hand, and also enhance the scattering effect of the particles on the light on the other hand, so that the light transmittance of the coating is obviously reduced finally.
Comparative example 3
Comparative example 3 was prepared exactly as in example 1, with the only difference that: the mass concentration of tetraethyl orthosilicate in the tetraethyl orthosilicate aqueous solution was adjusted to 0.5wt.%, 1.0wt.%, 1.5wt.%, and 2.0wt.%, respectively. At the same coating thickness, comparing fig. 9a, b and c, d, when the TEOS content is 0.5wt%, the three-dimensional network structure formed by the hydrolysis of TEOS increases the crosslinking strength of the coating, and a large amount of porous structure appears on the surface of the coating, further increasing the TEOS content, as shown in fig. 9c-f, as the three-dimensional network structure formed by the hydrolysis of TEOS in the coating increases, the crosslinking strength of the coating increases while the porous structure on the surface of the coating decreases, and the coating density increases. The results of a wear resistance test and a boiling resistance test show that the wear resistance and the boiling resistance of the coating are obviously improved along with the increase of the content of tetraethyl orthosilicate (TEOS); as shown in fig. 10, when the TEOS content is 2.0wt.%, the coating is slightly damaged after 300 times of friction, but no obvious scratch appears, and the contact angle of the friction region is 5.1 ° (fig. 11), so that the coating has excellent hydrophilicity and still shows good anti-fogging performance; as shown in fig. 12, when the TEOS content is 2.0wt.%, and the coating is boiled for 60 minutes, the coating still has a relatively dense structure, and no significant peeling occurs on the surface, and the contact angle of the coating surface is 5.2 ° (fig. 11), so that excellent hydrophilicity is shown, and the coating still has good antifogging performance.
Comparative example 4
Comparative example 4 was prepared identically to example 1, except that: the coating formed by the obtained coating is not added with polyacrylic resin emulsion, the thickness of the antifogging coating is 3.4 mu m, the water contact angle of a glass slide is close to 0 DEG, the light transmittance is 90.5%, and the coating can resist 220 revolutions of 250g load abrasion of a Taber abrasion tester and can resist boiling for 20 minutes. But the adhesion between the coating and the substrate is poor, is only 2.59MPa, and is difficult to bear longer-period abrasion and boiling time.
The coating formed by the organic-inorganic hybrid super-hydrophilic coating of example 1 (the thickness of the coating is 3.4 μm) is subjected to wear process failure analysis, as shown in fig. 5, after the coating is worn for 300 turns, only imprinting can be seen, no obvious scratch exists, only flattening and no peeling can be observed at the scratch position under high power, so that no substrate is exposed, the scratch resistance strength of the coating is improved, and a relatively complete structure can be maintained after the coating is worn for 300 turns.
In addition, the content of hydrophilic substances on the surface of the coating also influences the antifogging performance of the coating after friction. As shown in FIG. 6, the content of the S element on the surface of the coating is not obviously reduced compared with the original content in the abrasion process of 0-180 revolutions; when the coating is continuously worn to 240 turns, the content of the S element is reduced to a certain extent compared with the initial content, the reduction is matched with the change characteristics of the surface appearance of the coating, and the surface of the coating worn to 240 turns is damaged to a certain extent due to the occurrence of deep scratches, so that the hydrophilic substances in a small part of the area are lost; when the coating is worn to 300 turns, the S element content is obviously reduced to only 0.2 percent, because the coating is obviously peeled off at the moment, a large amount of surface hydrophilic substances are taken away, and the S element content on the surface is suddenly reduced.
The coating layer (the thickness of the coating layer is 3.4 μm) formed by the organic-inorganic hybrid super-hydrophilic coating material of example 1 was subjected to boiling process failure analysis, and as shown in fig. 7, the coating layer morphology after boiling for 60 minutes has little difference from the initial surface morphology, and almost no substrate is exposed. The results show that the cross-linking degree of the coating is improved, the coating has high structural stability and adhesive force with the substrate, and better structural integrity can be maintained for a longer time under the external force action of abrasion and boiling, so that the hydrophilic durability of the coating is improved.
The change of the S content of the surface characteristic element in the boiling stage of the coating is shown in FIG. 8. Different from the shape change rule, the S element is quickly lost 20 minutes before boiling, and the content is reduced from the initial 0.88% to below 0.3%; the boiling time is continuously increased, the content of the S element is always kept about 0.2 percent, and no obvious fluctuation occurs. This is mainly because most of the hydrophilic substances in the coating are lost to the water environment and form dynamic equilibrium after boiling for 20 minutes, so that the S element contained in the surface of the coating does not change in the subsequent boiling process. The WCA of the coating is maintained below 6 ℃ before 40 minutes of boiling, so that good antifogging performance can be maintained; after boiling for 50 minutes, the contact angle is increased to about 10 degrees, and the antifogging effect is obviously reduced.
The coating layer (the thickness of the coating layer is 3.4 μm) formed by the organic-inorganic hybrid super-hydrophilic coating material of example 1 was subjected to an acid and alkali resistance test: the coating is soaked in hydrochloric acid solution with the pH =2 and sodium hydroxide solution with the pH =13, the acid and alkali resistance of the coating is tested, the technical index (acid and alkali resistance for 6 hours) is taken as a reference standard, and the change of the WCA of the surface of the coating after the coating is soaked for different time is recorded.
As shown in fig. 13, it is understood that the coating has good acid and alkali resistance, and the acid resistance of the coating is more excellent than the alkali resistance. The WCA of the coating remained below 6 ° after 18 hours of soaking in the sodium hydroxide solution, while the WCA of about 6 ° remained after 72 hours of soaking in the hydrochloric acid solution. In addition, after the alkali resistance test of the coating, the whitening phenomenon of the inorganic coating after the alkali resistance test does not occur.
The coatings formed by the organic-inorganic hybrid super-hydrophilic coating of example 1 (thickness of coating layer 3.4 μm) were subjected to aging resistance test: the aging resistance of the coating is tested by adopting an accelerated aging test, and the specific operation method is that the coating is placed in an environment of 180 ℃, and the wettability of the surface of the coating is measured and recorded every 5 days.
As shown in fig. 14, it is understood that the coating layer still maintains a super-hydrophilic state after 25 days of the weathering test, and the contact angle does not exceed 6 °, and after 50 days of the weathering test, the contact angle is increased to 13.8 ℃, but the surface of the coating layer does not show changes in appearance such as yellowing and spots. Indicating that the coating has good aging resistance.
The coating layer (thickness of coating layer 3.4 μm) formed of the organic-inorganic hybrid superhydrophilic coating of example 1 was subjected to a heat resistance test: the coating was left at different temperatures for 90 minutes and its surface WCA was tested after it had cooled naturally. As shown in FIG. 15, the contact angles of the coatings were less than 6 ℃ after 90 minutes of treatment at 120 ℃, 160 ℃, 200 ℃, 240 ℃ and 280 ℃. The result shows that the coating has good heat resistance and can maintain the super-hydrophilicity within the temperature range of 0-280 ℃.
Claims (6)
1. A preparation method of organic-inorganic hybrid super hydrophilic emulsion is characterized by comprising the following steps:
(1) Adding 2-5 parts by mass of acidic silica sol into 100-200 parts by mass of water, adding hydrochloric acid into the water, and adjusting the pH value of the solution to 4-5;
(2) Adding 2-10 parts by mass of polyacrylic resin emulsion into the solution obtained in the step (1), and stirring to obtain a mixed solution;
(3) And (3) adding 0.1-2 parts by mass of tetraethyl orthosilicate aqueous solution into the mixed solution obtained in the step (2), reacting in a water bath at 50-60 ℃, adding 1-2 parts by mass of anionic surfactant after reaction, and uniformly mixing to obtain the organic-inorganic hybrid super-hydrophilic emulsion.
2. The method for preparing organic-inorganic hybrid superhydrophilic emulsion according to claim 1, characterized in that: in the step (1), the silica sol is O-type silica sol.
3. The method for preparing organic-inorganic hybrid superhydrophilic emulsion according to claim 1, characterized in that: in the step (1), the particle size of the silicon dioxide nano particles in the silica sol is 3-10 nm, and the solid content is not less than 20%.
4. The method for preparing organic-inorganic hybrid superhydrophilic emulsion according to claim 1, characterized in that: in the step (2), the mass concentration of the polyacrylic resin in the polyacrylic resin emulsion is not less than 3.0%.
5. The method for preparing organic-inorganic hybrid superhydrophilic emulsion of claim 1, characterized in that: in the step (3), the mass concentration of tetraethyl orthosilicate in the tetraethyl orthosilicate aqueous solution is not less than 2.0%.
6. The method for preparing organic-inorganic hybrid superhydrophilic emulsion according to claim 1, characterized in that: in the step (3), the anionic surfactant is sodium alkenyl sulfonate.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202211640530.3A CN115895367A (en) | 2022-12-20 | 2022-12-20 | Preparation method of organic-inorganic hybrid super-hydrophilic emulsion |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117887314A (en) * | 2024-01-16 | 2024-04-16 | 萨玛瑞汽车配件(盐城)有限公司 | Scratch-resistant and anti-fog automobile rearview mirror and preparation method thereof |
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| CN101941001A (en) * | 2009-07-03 | 2011-01-12 | 3M创新有限公司 | Hydrophilic coating, product, coating composition and method |
| CN102241939A (en) * | 2011-05-17 | 2011-11-16 | 华南理工大学 | Organic-inorganic hybrid super-hydrophilic coating as well as preparation method and application thereof |
| CN111574899A (en) * | 2020-06-12 | 2020-08-25 | 湖南航天三丰科工有限公司 | Organic-inorganic hybrid antifogging coating and preparation method thereof |
| CN113881252A (en) * | 2021-08-24 | 2022-01-04 | 东南大学 | Super-hydrophilic anti-fog coating with good durability and preparation method thereof |
| CN115074007A (en) * | 2022-05-12 | 2022-09-20 | 华南理工大学 | Inorganic-organic composite super-hydrophilic coating and preparation method and application thereof |
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| CN101941001A (en) * | 2009-07-03 | 2011-01-12 | 3M创新有限公司 | Hydrophilic coating, product, coating composition and method |
| CN102241939A (en) * | 2011-05-17 | 2011-11-16 | 华南理工大学 | Organic-inorganic hybrid super-hydrophilic coating as well as preparation method and application thereof |
| CN111574899A (en) * | 2020-06-12 | 2020-08-25 | 湖南航天三丰科工有限公司 | Organic-inorganic hybrid antifogging coating and preparation method thereof |
| CN113881252A (en) * | 2021-08-24 | 2022-01-04 | 东南大学 | Super-hydrophilic anti-fog coating with good durability and preparation method thereof |
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| CN117887314A (en) * | 2024-01-16 | 2024-04-16 | 萨玛瑞汽车配件(盐城)有限公司 | Scratch-resistant and anti-fog automobile rearview mirror and preparation method thereof |
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Inventor after: Zhang Youfa Inventor after: Nan Jiaqi Inventor after: Deng Weilin Inventor after: Su Yifan Inventor after: Xu Lili Inventor after: Li Haochen Inventor after: Yu Xinquan Inventor after: Zhang Churui Inventor before: Su Yifan Inventor before: Zhang Youfa Inventor before: Zhang Churui Inventor before: Li Haochen Inventor before: Nan Jiaqi Inventor before: Xu Lili Inventor before: Deng Weilin Inventor before: Yu Xinquan |