CN108516697A - Super-hydrophilic anti-reflection coating, preparation method and glass - Google Patents

Abstract

The invention relates to the technical field of functional materials, and discloses a method for preparing a superhydrophilic anti-reflection coating, comprising the following steps: (1) at room temperature, 1-100 parts by weight of a surfactant, 1000-20000 parts by weight of deionized water , 20-300 parts by weight of catalyst and 1000-20000 parts by weight of alcohol solvent are mixed to prepare mixed solution A; (2) at room temperature, 1-1000 parts by weight of tetraethyl orthosilicate and 0-1000 parts by weight of ethanol are mixed, After stirring evenly, the mixed solution B is prepared; (3) under the temperature condition of 15°C to 70°C, the mixed solution A is dropped into the mixed solution B, stirred and reacted for 0.5 to 10 hours, and the material is discharged to obtain a mixture with mesoporous properties. The _SiO2 spherical nanoparticle sol solution product whose diameter is 3～200nm is recorded as product C; (4) at room temperature, 100 parts by weight of product C and 1～20 parts by weight of pore-forming agent and 1～100 parts by weight of film-forming The additives are mixed and stirred evenly to obtain a mixture D; (5) the mixture D is coated on glass, and sintered at 300° C. to 600° C. to obtain a super-hydrophilic anti-reflection coating on the glass.

Description

A kind of superhydrophilic antireflection coating, preparation method and glass

technical field

The invention relates to the technical field of functional materials, in particular to a superhydrophilic antireflection coating, a preparation method and glass.

Background technique

The general preparation method of self-cleaning anti-fog glass is to cover a layer of organic or inorganic coating on the surface of the glass product, so that the glass surface produces a unique physical and chemical characteristics, so that the small droplets dropped on the glass surface are quickly flattened (super Hydrophilic properties), that is, the contact angle of small water droplets on the glass surface is close to zero, forming a uniform water film, which will not affect the mirror image and light transmission, and take away the stains through the gravity drop of the uniform water film, Achieve self-cleaning effect. Glass anti-reflection is to coat a layer of film on the surface of the glass, so that the two beams of light reflected on the upper and lower surfaces of the film produce destructive interference, the reflected light disappears, and the transmitted light is enhanced. The key to the preparation of high-performance anti-reflection coatings is to design nano-coatings with low refractive index.

If the car windshield and rearview mirror are made of super-hydrophilic anti-reflection glass, a uniform water film (not water droplets) can be formed on the glass surface in rainy days to maintain good light transmission and mirror imaging, thereby greatly increasing the driving time. Safety. The cleaning of window glass in high-rise buildings is a tricky and dangerous task, but if it is made of super-hydrophilic self-cleaning glass, it can be kept clean by washing with rainwater or tap water, greatly reducing labor intensity. If self-cleaning antireflection glass is used on the surface of the solar panel, the utilization rate of solar energy can be greatly improved. First, the antireflection effect of the coating can reduce the reflection of sunlight and increase the absorption of sunlight. Second, the self-cleaning effect can prevent the surface of the solar panel from being dusty, Pollution by stains leads to a decrease in the utilization rate of sunlight from solar panels.

At present, there are photo-induced super-hydrophilic TiO ₂ coated glass on the market. The photocatalytic properties of TiO ₂ are used to improve the hydrophilicity of the glass surface. It will show good hydrophilic performance, but there is no such effect in a dark environment. Furthermore, the _TiO2 film does not reach the super-hydrophilic standard (that is, the contact angle is less than 5°), and the light transmission is not good. In addition, some people have successfully prepared a super-hydrophilic anti-fog porous silica coating. Although the coating has excellent super-hydrophilic anti-fog performance, the visible light transmittance is lower than 90%, and the preparation process is complicated. Therefore, it is of great practical significance to provide a method for preparing a super-hydrophilic self-cleaning, anti-fog and anti-reflective glass coating with simple process, low cost and stable performance.

Contents of the invention

The purpose of the present invention is to provide a super-hydrophilic antireflection coating, a preparation method and glass. The preparation method has easy-to-obtain raw materials, simple equipment and process, and low cost, and the prepared glass has high hardness, is not easy to be scratched, and has extremely high light transmittance and superhydrophilicity.

A preparation method for a super-hydrophilic anti-reflection coating, comprising the following steps:

(1) At room temperature, mix 1-100 parts by weight of a surfactant, 1000-20000 parts by weight of deionized water, 20-300 parts by weight of a catalyst and 1000-20000 parts by weight of an alcoholic solvent to prepare a mixed liquid A;

(2) At room temperature, mix 1-1000 parts by weight of tetraethyl orthosilicate and 0-1000 parts by weight of ethanol, and stir evenly to prepare mixed solution B;

(3) Under the temperature condition of 15°C-70°C, drop the mixed solution A into the mixed solution B, stir and react for 0.5-10 hours, and discharge the material to obtain a mesoporous _SiO2 sphere with a diameter of 3-200nm Nanoparticle sol solution product, denoted as product C;

(4) At room temperature, mix 100 parts by weight of the product C with 1-20 parts by weight of a pore-forming agent and 1-100 parts by weight of a film-forming aid, and stir evenly to obtain a mixture D;

(5) The mixture D is coated on the glass, and sintered at 300° C. to 600° C. to obtain a super-hydrophilic anti-reflection coating on the glass.

While the superhydrophilic antireflection coating is prepared by the above preparation method, the superhydrophilic self-cleaning antireflection glass is also prepared.

Preferably, the thickness of the super-hydrophilic anti-reflection coating is 200-5000 nm.

Preferably, the catalyst described in step (1) is one or more combinations of concentrated ammonia water, hydrochloric acid, sodium hydroxide, triethanolamine, triethylamine, nitric acid, acetic acid, phosphoric acid, boric acid, and sulfuric acid.

Preferably, the alcoholic solvent described in step (1) is one or a combination of ethanol, methanol, isopropanol, n-butanol, ethylene glycol, and propylene glycol.

Preferably, the surfactant described in step (2) is cetyltrimethylammonium bromide, cetyltrimethylammonium chloride, dodecyltrimethylammonium bromide, dodecyltrimethylammonium Sodium sulfate, sodium dodecylbenzenesulfonate, polyoxyethylene-polyoxypropylene-polyoxyethylene triblock polyether (F127), alkylphenol polyoxyethylene ether (APEO), high-carbon fatty alcohol polyoxygen Vinyl ether (AEO), fatty acid polyoxyethylene ester (AE), fatty acid methyl ester ethoxylate (FMEE), polypropylene glycol ethylene oxide adduct, alcohol ether sulfate (AES), alcohol ether phosphate, One or a combination of alcohol ether sulfates (AS), sorbitan esters, citric acid, citric acid esters, alkanolamides, and sucrose esters.

Preferably, the pore forming agent described in step (4) is benzoic acid, citric acid, citrate, sodium lauryl sulfate, cetyltrimethylammonium bromide, polyvinyl alcohol, white dextrin, One or a combination of stearic acid, ammonium bicarbonate, polyethylene glycol, urea, and paraformaldehyde.

Preferably, the film-forming aid described in step (4) is diisobutyl ketone, N,N-dimethylformamide, ethylene glycol monobutyl ether, butyl acrylate, dimethyl succinate, pentadiene Dimethyl adipate, dimethyl adipate, ethylene glycol ethyl ether, cyclohexanone, polyvinyl alcohol, n-butanol, dipropylene glycol propyl ether, dipropylene glycol dimethyl ether or a combination of more than one.

Preferably, the method of coating the mixture D on the glass in step (5) includes dipping, brushing or spraying.

Preferably, the sintering time is 0.5-8 hours.

Another object of the present invention is to disclose a super-hydrophilic anti-reflection coating prepared by the above-mentioned preparation method.

Another object of the present invention is to disclose a super-hydrophilic self-cleaning anti-reflection glass, which contains the super-hydrophilic anti-reflection coating prepared by the above preparation method.

The super-hydrophilic anti-reflection coating of the present invention is assembled from inorganic mesoporous silicon dioxide nanoparticles, and the coating surface has a multi-level composite hole structure. The multi-level composite hole structure is composed of internal holes of the mesoporous silica nanoparticles and interstitial holes between the mesoporous silica. The size of the internal pores of the mesoporous silica nanoparticles is 0.2-40nm. The interstitial pores between the mesoporous silica are generated by removing the pore-forming agent, and the size thereof is 1-150nm.

Compared with the prior art, the present invention has the following beneficial effects:

The present invention removes the pore-forming agent and the film-forming aid to obtain the interstitial pores between the mesoporous silica through sintering, and removes the surfactant in the mesoporous at the same time to obtain the internal pores of the mesoporous silica nanoparticles, a one-step method Realize the formation of multi-level holes. The special composite pore structure of the invention endows the coating with excellent superhydrophilic performance, high transparency, remarkable self-cleaning and anti-reflection effects.

The preparation method of the invention has easy-to-obtain raw materials, simple equipment and process, and low cost.

The super-hydrophilic anti-reflection coating of the present invention has extremely high light transmittance and super-hydrophilicity at the same time: the light transmittance is as high as 95.0-98.5%, and the contact angle of the coating to water in air is 0-5°.

The super-hydrophilic anti-reflection coating of the invention has high hardness and is not easy to be scratched, and can be used on glass products requiring self-cleaning, anti-fog treatment and anti-reflection.

Description of drawings

Fig. 1 is the schematic diagram that the coating that the embodiment of the present invention 1 makes has superhydrophilicity;

FIG. 2 is a transmission electron microscope image of mesoporous nano _{- SiO2} particles prepared from SiO2 spherical nanoparticle sol solution product in Example 1 of the present invention.

Detailed ways

The present invention will be further described below in conjunction with the examples, but it should be noted that the examples do not limit the protection scope of the present invention.

Example 1: 1g of cetyltrimethylammonium bromide, 100ml of deionized water, 0.4g of sodium hydroxide and 100ml of ethanol were mixed uniformly and stirred for 10min (to obtain mixed solution A), and 30ml of ethanol, 8g of orthosilicic acid Ethyl esters were mixed and stirred for 10 minutes (to obtain mixed solution B), and mixed solution B was dropped into mixed solution A at a rate of 1 drop per second, and reacted at 15°C (magnetic stirring) for 2 hours to obtain _SiO2 spherical nanoparticle sol solution Product (Product C). Take 50ml of product C in a beaker, add 10ml of n-butanol and 2g of PEG, stir for 10 minutes, and smear the glass surface. The thickness of the coating is 200-5000nm. The coating methods include: dipping, brushing or spraying. Sintering was performed after curing for 30 min. The sintering temperature is 300°C-600°C, and the sintering time is 0.5-8 hours. The resulting coating is superhydrophilic, as shown in Figure 1.

Wherein, the prepared SiO sol was subjected to centrifugation washing, deionized water and ethanol were used for centrifugal washing, 5% hydrochloric acid aqueous solution was added to the centrifuged SiO ₂ , and the reaction was carried out _at 80° C. for 20 h to obtain mesoporous nano-SiO ₂ particles. Observation was carried out with a transmission electron microscope, as shown in Figure 2.

Example 2: 2g of alcohol ether phosphate, 100ml of deionized water, 1g of concentrated ammonia and 50ml of isopropanol were mixed uniformly and stirred for 10min (to obtain mixed solution A), 500ml of ethanol and 10g of ethyl orthosilicate were mixed and stirred for 10min (to obtain mixed solution B), mixed solution B was dripped into mixed solution A at a rate of 1 drop per second, and reacted at 50 ° C (magnetic stirring) for 5 hours to obtain _SiO2 Spherical nanoparticle sol solution product (product C). Take 50ml of product C in a beaker, add 35ml of diisobutyl ketone, 5ml of N,N-dimethylformamide, 4g of PEG, stir for 10 minutes and then smear the glass surface. The thickness of the coating is 200-5000nm. The coating methods include: Dip, brush or spray. Sintering was performed after curing for 30 min. The sintering temperature is 300°C-600°C, and the sintering time is 0.5-8 hours.

Example 3: 2g sodium dodecylbenzenesulfonate, 50ml deionized water, 0.02g nitric acid and 20ml n-butanol were mixed uniformly and stirred for 10min (to obtain mixed solution A), 150ml ethanol, 2g orthosilicate ethyl Mix and stir for 10min (to obtain mixed solution B), mixed solution B is dripped in mixed solution A at a speed of 1 drop per second, and react at 25°C (magnetic stirring) for 10h to obtain SiO _spherical nanoparticle sol solution product ( Product C). Take 50ml of product C in a beaker, add 100ml of n-butanol, 5ml of ethylene glycol monobutyl ether, and 4g of citric acid, stir for 10 minutes and then smear the glass surface. The thickness of the coating is 200-5000nm. The coating methods include: dip coating method , brushing or spraying. Sintering was performed after curing for 30 min. The sintering temperature is 300°C-600°C, and the sintering time is 0.5-8 hours.

Example 4: Mix 2g alkylphenol polyoxyethylene ether, 50ml deionized water, 3g triethanolamine and 200ml ethylene glycol and stir for 10min (to obtain mixed solution A), mix 60ml ethanol and 5g methyl orthosilicate And stir 10min (obtain mixed solution B), mixed solution B is dripped in the mixed solution A with the speed of 1 drop per second, at 30 ℃ (magnetic stirring) reaction 0.5h, obtains SiO _Spherical nanoparticles sol solution product ( Product C). Take 50ml of product C in a beaker, add 1ml of N,N-dimethylformamide, 5ml of ethylene glycol monobutyl ether, and 10g of hexadecyltrimethylammonium bromide, stir for 10 minutes, and then smear the glass surface. The thickness is 200-5000nm, and the coating method includes: dip coating method, brush coating method or spray coating method. Sintering was performed after curing for 30 min. The sintering temperature is 300°C-600°C, and the sintering time is 0.5-8 hours.

Example 5: Mix 2g of alkanolamide, 50ml of deionized water, 2.5g of boric acid and 150ml of isopropanol and stir for 10min (to obtain mixed solution A), mix 320ml of ethanol and 8g of methyl orthosilicate and stir for 10min (to obtain mixed solution B), mixed solution B was dripped into mixed solution A at a rate of 1 drop per second, and reacted at 50°C (magnetic stirring) for 7h to obtain _SiO2 Spherical nanoparticle sol solution product (product C). Take 50ml of product C in a beaker, add 50ml of dimethyl succinate, 5ml of ethylene glycol monobutyl ether, and 20g of ammonium bicarbonate, stir for 10 minutes and then smear the glass surface. The thickness of the coating is 200-5000nm. The coating method includes: : dipping method, brushing method or spraying method. Sintering was performed after curing for 30 min. The sintering temperature is 300°C-600°C, and the sintering time is 0.5-8 hours.

Example 6: Mix 2g fatty acid methyl ester ethoxylate, 50ml deionized water, 0.8g phosphoric acid and 80ml propylene glycol and stir for 10min (to obtain mixed solution A), mix and stir 80ml ethanol and 6g methyl orthosilicate 10min (to obtain mixed solution B), drop mixed solution B into mixed solution A at a rate of 1 drop per second, and react at 70°C (magnetic stirring) for 2h to obtain _SiO2 Spherical nanoparticle sol solution product (product C) . Take 50ml of product C in a beaker, add 80ml of dipropylene glycol propyl ether, 5ml of ethylene glycol monobutyl ether, and 1g of paraformaldehyde, stir for 10 minutes and then smear the glass surface. The thickness of the coating is 200-5000nm. The coating method includes: Paint, brush or spray. Sintering was performed after curing for 30 min. The sintering temperature is 300°C-600°C, and the sintering time is 0.5-8 hours.

The coatings prepared on glass in Examples 1-6 are superhydrophilic antireflection coatings, and the glass containing the coatings is superhydrophilic self-cleaning antireflection glass.

The performance of the super-hydrophilic antireflection coating that embodiment 1～6 makes is as shown in table 1:

Table 1 Coating Properties

As can be seen from Table 1, the superhydrophilic antireflection coating of the present invention has extremely high light transmittance and superhydrophilicity simultaneously: the light transmittance is as high as 95.0～98.5%, and the contact angle of the coating to water in air It is 0~5°. The super-hydrophilic anti-reflection coating of the invention has high hardness and is not easy to be scratched, and can be used on glass products requiring self-cleaning, anti-fog treatment and anti-reflection.

The preparation method of the invention has easy-to-obtain raw materials, simple equipment and process, and low cost. By sintering, remove the pore-forming agent and film-forming aid to obtain interstitial pores between mesoporous silica, and remove the surfactant in the mesoporous pores to obtain the internal pores of mesoporous silica nanoparticles. One-step method to achieve multiple Formation of level holes. The special composite pore structure of the invention endows the coating with excellent superhydrophilic performance, high transparency, remarkable self-cleaning and anti-reflection effects.

The technical solutions provided by the embodiments of the present invention have been introduced in detail above, and the principles and implementation modes of the embodiments of the present invention have been explained by using specific examples in this paper. The descriptions of the above embodiments are only applicable to help understand the embodiments of the present invention At the same time, for those of ordinary skill in the art, according to the embodiment of the present invention, there will be changes in the specific implementation and application scope. In summary, the content of this specification should not be construed as limiting the present invention.

Claims (10)

1. a kind of preparation method of super hydrophilic antireflecting coating, which is characterized in that include the following steps：

(1) at room temperature, by 1~100 parts surfactant, 1000~20000 parts by weight of deionized water, 20~300 weight Part catalyst and the mixing of 1000~20000 parts by weight alcohols solvents, are made mixed liquor A；

(2) at room temperature, 1~1000 parts by weight ethyl orthosilicate and 0~1000 parts by weight of ethanol are mixed, after stirring evenly, system Obtain mixed liquid B；

(3) under 15 DEG C~70 DEG C temperature conditions, mixed liquor A is added dropwise in mixed liquid B, is stirred to react 0.5~10 hour, goes out Material, obtains the SiO of a diameter of 3~200nm with mesoporous property₂Nano spherical particle sol solution product, is denoted as product C；

(4) at room temperature, 100 parts by weight product C are mixed with 1~20 parts by weight pore creating material and 1~100 parts by weight coalescents, It stirs evenly, obtains mixture D；

(5) mixture D is coated on glass, is sintered at 300 DEG C~600 DEG C, super hydrophilic antireflecting coating is obtained on glass.

2. a kind of preparation method of super hydrophilic antireflecting coating according to claim 1, which is characterized in that the super hydrophilic increasing The thickness of antireflective coating layer is 200~5000nm.

3. a kind of preparation method of super hydrophilic antireflecting coating according to claim 1, which is characterized in that step (1) is described Catalyst be concentrated ammonia liquor, hydrochloric acid, sodium hydroxide, triethanolamine, triethylamine, nitric acid, acetic acid, phosphoric acid, boric acid, sulfuric acid one kind Or more than one combination.

4. a kind of preparation method of super hydrophilic antireflecting coating according to claim 1, which is characterized in that step (1) is described Alcohols solvent be ethyl alcohol, methanol, isopropanol, n-butanol, ethylene glycol, propylene glycol one or more kinds of combinations.

5. a kind of preparation method of super hydrophilic antireflecting coating according to claim 1, which is characterized in that step (2) is described Surfactant be cetyl trimethylammonium bromide, hexadecyltrimethylammonium chloride, dodecyl trimethyl ammonium bromide, Lauryl sodium sulfate, neopelex, polyoxyethylene-poly-oxypropylene polyoxyethylene triblock polyether (F127), alkane Base phenol polyethenoxy ether (APEO), high-carbon fatty alcohol polyoxyethylene ether (AEO), polyoxyethylene carboxylate (AE), fatty acid methyl Ester ethoxylate (FMEE), the ethylene oxide adduct of polypropylene glycol, ether alcohol sulfate (AES), alcohol ether phosphate, alcohol ether sulphur It is one or more kinds of in acid esters salt (AS), sorbitan ester, citric acid, citrate, alkylolamides, sucrose ester Combination.

6. a kind of preparation method of super hydrophilic antireflecting coating according to claim 1, which is characterized in that step (4) is described Pore creating material be benzoic acid, citric acid, citrate, lauryl sodium sulfate, cetyl trimethylammonium bromide, polyethylene One or more kinds of combinations in alcohol, white dextrin, stearic acid, ammonium hydrogen carbonate, polyethylene glycol, urea, paraformaldehyde.

7. a kind of preparation method of super hydrophilic antireflecting coating according to claim 1, which is characterized in that step (4) is described Coalescents be isobutyrone, N,N-dimethylformamide, ethylene glycol monobutyl ether, butyl acrylate, succinic acid diformazan Ester, dimethyl glutarate, dimethyl adipate, ethylene glycol ethyl ether, cyclohexanone, polyvinyl alcohol, n-butanol, dipropylene glycol propyl ether, One or more kinds of combinations of dimethyl ether.

8. a kind of preparation method of super hydrophilic antireflecting coating according to claim 1, which is characterized in that will in step (5) Mixture D is coated in the coating method on glass：Dip coating, spread coating or spray coating method；Sintering time is 0.5~8 hour.

9. super hydrophilic antireflecting coating made from the preparation method as described in any one of claim 1~8.

10. a kind of superhydrophilic self-cleaning anti-reflective glass, which is characterized in that containing as claimed in claim 9 super close on the glass Water antireflecting coating.