CN107902918B

CN107902918B - Preparation method of anti-reflection and anti-reflection film layer

Info

Publication number: CN107902918B
Application number: CN201711290403.4A
Authority: CN
Inventors: 康煌; 柯城; 贾迎辉; 邬亚斌; 李弥滋
Original assignee: Fuyao Glass Industry Group Co Ltd
Current assignee: Fuyao Glass Industry Group Co Ltd
Priority date: 2017-12-08
Filing date: 2017-12-08
Publication date: 2020-03-31
Anticipated expiration: 2037-12-08
Also published as: CN107902918A

Abstract

The invention discloses a preparation method of an anti-reflection film layer, which comprises the following steps: A. taking silicon alkoxide, an alcohol solvent and a silane coupling agent, mixing and stirring to obtain a mixed solution A; B. mixing and stirring an acid catalyst and deionized water to obtain a mixed solution B; C. slowly dripping the mixed solution B into the mixed solution A to prepare silica sol; D. mixing and stirring silica sol, hollow silica particles and a dispersing agent to prepare a coating solution; E. selecting a glass substrate, polishing, cleaning and drying; F. coating the coating solution on a glass substrate, and after leveling, drying and curing to form a film layer; G. and putting the glass substrate in an alkaline solution for corrosion, forming a concave-convex suede surface on the surface of the corroded film layer, and then cleaning and drying to obtain the coated glass. The antireflection film layer prepared by the method has a hollow hole structure inside and a concave-convex suede surface on the surface, and the average reflectivity can be reduced to below 2%.

Description

Preparation method of anti-reflection and anti-reflection film layer

The technical field is as follows:

the invention belongs to an antireflection film layer technology, and particularly relates to a method for an antireflection film layer.

Background art:

with the widespread use of glass, there is an increasing demand for reducing the reflectivity of the glass surface. For ordinary glass, the reflectivity is generally 8% -10%, so that the surface of the glass presents the reflection of an object on one side of an observer, the observation of the observer on the object on the other side of the glass is influenced, and the problems are particularly prominent in application scenes such as exhibition counter glass application, display screen glass application, objects in a car with the reflection of a front windshield of a car at night and the like, and the visual fatigue of people is easily caused. In order to reduce visual fatigue and overcome glare, antireflection glasses capable of reducing the reflectance of light have been developed.

The antireflection glass is one kind of glass with specially treated surface. The antireflection glass is prepared by processing one or two surfaces of a high-quality glass sheet by a special process, so that the antireflection glass has lower reflectivity compared with common glass. The concept of antireflection includes two aspects, one is to reduce the mirror effect of the glass surface, convert the mirror reflection of light into diffuse reflection, and to achieve this effect, the glass surface etching is usually realized by a method of etching the glass surface, the glass surface etching is usually performed by hydrofluoric acid or other mixed acid-base etching, because the glass is processed on the silicon dioxide material of the glass itself, the hydrofluoric acid is basically selected because of high etching efficiency, but the hydrofluoric acid is a local toxic substance, and the strong corrosivity and volatility of the hydrofluoric acid determine that the production safety must be ensured by depending on external equipment and processes, which is not beneficial to large-scale production, and other acid-base etching is adopted, the process has the defect of long etching time, generally more than 20 hours is needed, and the efficiency is very low.

On the other hand, the reflection of incident light is reduced and the transmission is increased through the principle of light interference, and in effect, the transparency is improved. This is usually achieved by glass surface coating techniques. The sol-gel process is commonly used in the prior art to plate the glue solution of various liquid materials after full reaction on glass, and has the advantages of uniform components of various materials after mixing reaction, capability of ensuring the uniformity of a film layer and capability of changing the performance of the film layer by adjusting the proportion of raw materials. The silicon dioxide antireflection film is the most commonly used antireflection film at present and is generally realized by adding hollow silicon dioxide particles into silica sol to form a film.

For example, chinese patent application No. 201110363911.7 discloses a porous silica antireflection film and a method for manufacturing the same, in which an antireflection film layer is formed on a glass surface, and hollow silica particles are added to make the antireflection film layer have an internal hollow pore structure, so that the film layer has a good antireflection effect during use. But practice proves that the adding amount of hollow silicon dioxide particles is not well controlled in the film layer, the effect of reducing the reflectivity is not ideal due to less added particles, the haze of the film layer is increased and the transparency is reduced due to more added or uneven distribution, and the problem that the salt fog resistance and the weather resistance of the existing antireflection film layer are mutually restricted with the antireflection performance is solved because the film layer must have certain porosity for reducing the refractive index of the antireflection film layer, but the porosity causes loose structure of the film layer and reduced bonding force, so that the film layer cannot be normally used, therefore, the refractive index of the antireflection film layer prepared by the method is too low, the reflectivity of glass applying the antireflection film layer in a visible light wave band of 380 nm-780 nm can be reduced to about 2% -4%, and for products such as automobile glass, locomotive glass, aircraft glass and the like with increasingly higher antireflection requirements, it is increasingly difficult to meet the demand.

The invention content is as follows:

the invention aims to provide a preparation method and a product for preparing an antireflection film layer on the surface of glass by a method of firstly preparing the antireflection film layer by a sol-gel method and then corroding the antireflection film layer by an alkaline solution.

The technical solution of the invention is as follows:

a preparation method of an anti-reflection film layer is characterized by comprising the following steps:

A. mixing and stirring silicon alkoxide, an alcohol solvent and a silane coupling agent in a molar ratio of 1 (1-20) to 0.01-5 to obtain a mixed solution A;

B. mixing and stirring an acid catalyst and deionized water in a molar ratio of (0.001-0.05) to (1-30) to obtain a mixed solution B;

C. slowly dripping the mixed solution B into the mixed solution A, keeping the mixed solution A in a continuously stirred state until the dripping of the mixed solution B is finished, and standing to obtain silica sol C;

D. mixing and stirring silica sol C, hollow silica particles and a dispersing agent in a mass ratio of 1 (0.01-0.5) to 0.01-0.5 to prepare a coating solution D;

E. selecting a glass substrate, polishing the surface of the glass substrate by using a polishing solution, then washing the glass substrate clean by using deionized water, then sequentially ultrasonically cleaning the glass substrate for 10 minutes by using acetone and absolute ethyl alcohol, taking out the glass substrate, and putting the glass substrate into a 60 ℃ drying oven for drying;

F. coating the coating solution D on a glass substrate by adopting a roll coating method, drying the glass substrate for 10-40 min under the condition of controlling the surface temperature of the glass substrate to be 50-70 ℃ after a film layer on the surface of the glass substrate is leveled, curing for 10-60 min under the condition of 180-220 ℃, and forming a film layer F on the surface of the glass substrate;

G. and (3) placing the glass substrate with the film layer F in an alkaline solution for corrosion for 20-30 min at the corrosion temperature of 20-40 ℃, forming a concave-convex suede surface on the surface of the corroded film layer F, cleaning the surface with deionized water, and drying to obtain the coated glass with the anti-reflection film layer.

The molar ratio of the mixed solution is changed according to the different types of the added substances, the hydrolysis and polymerization rates and the particle size of the silicon alkoxide can be controlled by controlling the using amounts and the adding rates of the added acid catalyst and the deionized water, the added acid catalyst and the deionized water are too little, the hydrolysis degree of the silicon alkoxide is low, and the obtained silicon dioxide colloid is little; the acid catalyst and the deionized water are added too much, the adding speed is too fast, the hydrolysis and the polycondensation of the silicon alkoxide are too fast, the precipitate is easy to form, the sol can not be obtained, and the hydrolysis speed of the silicon alkoxide and the properties of a subsequent film layer are controlled by the added alcohol solvent. If the solvent amount is small, the silicon alkoxide is hydrolyzed too fast, and meanwhile, the subsequent film layers are easy to have orange peel and other problems; the amount of the alcohol solvent is large, and the subsequent film layer is easy to crack. The silicon alkoxide is continuously hydrolyzed and polymerized by the acid catalyst to obtain sols with different properties and network structures thereof, after the film is formed on the surface of the glass by the coating liquid, appropriate acting force is exerted among oxide particles, if the bonding among the particles is weaker, the porous structure is favorably formed, the refractive index can be greatly reduced, but the strength is poor, the coating liquid is not wear-resistant, and if the bonding among the particles is strong, the mechanical property and the wear-resistant capability can be greatly improved, but the refractive index of the film layer is higher and the anti-reflection effect is poor.

Wherein, the silicon alkoxide is selected from one or a mixture of two of ethyl orthosilicate and methyl orthosilicate. The silicon alkoxide is used as a silicon element source, has the advantage of easy acquisition and is easy for large-scale production.

Wherein the alcohol solvent is selected from one of methanol, ethanol, propanol and butanol. The solvent has the characteristic of easy intermiscibility with silicon alkoxide, and simultaneously has good intermiscibility with subsequent additives, so that the prepared antireflection film has uniform properties, and various leveling problems are not generated.

Wherein the silane coupling agent is selected from KH550, KH560 and KH 570. Because the silane coupling agent molecules have two functional groups of organophilic group and organophilic group, the silane coupling agent molecules can be used as a 'molecular bridge' for connecting inorganic materials and organic materials, and two materials with different properties are connected, namely an inorganic phase-silane coupling agent-organic phase combined layer is formed, so that the binding force between the antireflection film layer and the glass is increased.

Wherein, the acid catalyst is selected from one or a mixture of two of hydrochloric acid and nitric acid. The acid catalyst is used for assisting hydrolysis of silanol, under the action of different acid catalysts, the agglomeration degree of silica colloids obtained after hydrolysis is different, the corrosion resistance degree of the prepared film layer after curing is different, and the acid catalyst can be used for regulating and controlling the corrosion morphology of the film layer to obtain different porosities.

Wherein the dispersant is selected from one of Disperbyk2050, Disperbyk185, Disperbyk171 and Disperbyk 174. The used dispersing agent is suitable for dispersing nano particles in a water-alcohol system, plays a role in dispersing through the steric hindrance effect of a high molecular polymer, and does not influence the nano particles dispersed in a solution when the potential or the acidity and alkalinity are changed in the solution preparation process.

Wherein the alkaline solution is selected from one or a mixture of any two of NaOH solution, KOH solution and LiOH solution. According to different properties of the prepared film, different alkaline solutions are adopted for corrosion.

Wherein, the hollow silica particles are selected from one or more of the following combinations: spherical hollow silica particles, hemispherical hollow silica, ellipsoidal hollow silica particles, and cylindrical hollow silica particles. The regular geometry facilitates the dispersed suspension of the hollow silica particles in solution.

Wherein the concentration of the alkaline solution is 0.01-0.5 mol/L. If the concentration of the alkaline solution is too low, the corrosion effect is too weak, the surface of the film layer is difficult to form a concave-convex suede, if the concentration is too high, the corrosion is too severe, pores with large pore diameters are easy to cause, and the film layer is damaged.

The porosity of the antireflection film layer is 25.7% -57.1%, and the thickness of the antireflection film layer is 100-200 nm.

The principle of the invention is as follows:

the preparation method comprises the steps of firstly preparing coating liquid by a sol-gel method, coating the coating liquid on the surface of glass to form an antireflection film layer, and then corroding the antireflection film layer by a surface corrosion technology to form a concave-convex suede surface, wherein the film layer is low in corrosion resistance, so that the film layer is etched by using a weak-corrosion alkaline solution; the anti-reflection film layer obtained through the steps not only has a hollow hole structure formed by doping hollow silica particles inside, but also has a concave-convex suede surface with corroded surface, as shown in figure 1, so that the refractive index of the film layer is further reduced, and the glass coated with the anti-reflection film layer has lower reflectivity.

Due to the adoption of the technical scheme, the invention has the following beneficial effects:

1. the anti-reflection film layer prepared by the invention has a hollow hole structure inside and a concave-convex suede surface on the surface, so that the average reflectivity of the glass coated with the anti-reflection film layer can be reduced to below 2% on a visible light wavelength spectrum of 380-780 nm.

2. The invention adopts weak corrosive alkali solution to corrode the surface of the film layer, thereby not only having low cost and high corrosion speed, but also realizing no pollution discharge by neutralizing and discharging the weak alkali solution, and causing no harm to human bodies and environment.

3. The preparation process is simple and easy to operate, the raw materials are cheap and easy to obtain, the reaction process basically has no industrial three wastes, and the preparation method has the characteristics of environmental protection, low energy consumption, high benefit and the like and is suitable for industrial production.

Description of the drawings:

FIG. 1 is a schematic view of the structure of an antireflective coating of the invention;

description of reference numerals:

1. the glass substrate, 2, antireflection coating, 3, hollow silica particles, 4, unsmooth matte.

The specific implementation mode is as follows:

the present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the present invention.

As shown in fig. 1, an antireflection film layer 2 formed on the surface of a glass substrate 1 by the preparation method of the present invention has a hollow pore structure containing hollow silica particles 3, and the surface is etched into a concave-convex textured surface 4 by an alkaline solution.

Example 1

(1) Weighing absolute ethyl alcohol, tetraethoxysilane and KH560 with the molar ratio of 1:10.6:3.7, and uniformly mixing and stirring under the action of a magnetic stirrer to obtain a mixed solution A; weighing nitric acid and deionized water with the mass fraction of 10% and the molar ratio of 0.002:11, and uniformly mixing and stirring under the action of a magnetic stirrer to obtain a mixed solution B; and slowly dripping the mixed solution B into the mixed solution A by using a dropper, continuously stirring the mixed solution A in the dripping process until the mixed solution A and the mixed solution A are completely mixed, continuously stirring for 5 hours, and standing for 1 day to obtain the silica sol.

(2) Weighing 3.6g of polyacrylic acid with molecular weight of 2000, dissolving the polyacrylic acid in 20mL of ammonia water, obtaining a mixed solution C after the polyacrylic acid is completely dissolved, adding the mixed solution C into 300mL of absolute ethyl alcohol, uniformly stirring and mixing under magnetic stirring, dropwise adding 0.2mL of ethyl orthosilicate by a pipette every 20min for 15 times, continuously stirring for 5 hours after completion, obtaining hollow silica particles with average particle size of 60nm and average shell thickness of 12nm, respectively centrifugally washing the hollow silica particles for 3 times by using deionized water and absolute ethyl alcohol, and then reserving the hollow silica particles for later use.

(3) Weighing silica sol, hollow silica particles and Disperbyk-171 in a mass ratio of 1:0.05:0.01, and mixing and stirring for 1 hour under magnetic stirring to obtain a coating solution.

(4) A glass substrate with the size of 100mm multiplied by 3mm (length multiplied by width multiplied by thickness) is taken, the surface of the glass is polished by polishing solution prepared by cerium oxide, then the glass is washed clean by deionized water, and then the glass substrate is cleaned by acetone and absolute ethyl alcohol for 10 minutes in an ultrasonic mode in sequence, and then the glass substrate is taken out and is placed into a 60 ℃ oven to be dried for later use.

(5) In a hundred-grade dust-free operation room, 3g of coating solution is coated on the surface of the cleaned glass by a wire bar coater, the glass is kept stand for 20 minutes, after a film layer on the surface of the glass substrate is leveled, the film layer is dried by an infrared lamp with the power of 1.5kw, the surface temperature of the glass is controlled at 50 ℃, and the glass substrate is placed in an oven with the temperature of 200 ℃ for curing for 30 minutes after drying.

(6) And taking out the glass substrate from the oven after the temperature of the glass substrate is reduced to room temperature, putting the glass substrate into a mixed solution of 0.1mol/L NaOH and 0.1mol/L KOH for corrosion, wherein the corrosion time is 30min, and the temperature of the corrosive liquid is 40 ℃. And taking out the corroded glass substrate, and cleaning the glass substrate with water to obtain the anti-reflection and anti-reflection film layer with the porous structure on the glass substrate.

Example 2

(1) Weighing ethyl orthosilicate, absolute ethyl alcohol and KH570 with the molar ratio of 1:12:2.3, and uniformly mixing and stirring under the action of a magnetic stirrer to obtain a mixed solution A; weighing hydrochloric acid and deionized water with the mass fraction of 30% and the molar ratio of 0.004:15, and uniformly mixing and stirring under the action of a magnetic stirrer to obtain a mixed solution B; and slowly dripping the mixed solution B into the mixed solution A by using a dropper, continuously stirring the mixed solution A in the dripping process until the mixed solution A and the mixed solution A are completely mixed, continuously stirring for 5 hours, and standing for 1 day to obtain the silica sol.

(3) Weighing silica sol, hollow silica particles and Disperbyk-174 in a mass ratio of 1:0.1:0.05, and mixing and stirring for 1 hour under the action of a magnetic stirrer to obtain a coating solution.

(5) In a hundred-grade dust-free operation room, 3g of coating solution is taken, a wire bar coater is used for coating the surface of the cleaned glass, the glass is kept stand for 20 minutes, after a film layer on the surface of the glass substrate is leveled, the film layer is dried by an infrared lamp with the power of 1.5kw, the surface temperature of the glass is controlled at 70 ℃, and the glass substrate is placed in an oven with the temperature of 180 ℃ for curing for 60 minutes after drying.

(6) And taking out the glass substrate from the oven after the temperature of the glass substrate is reduced to room temperature, putting the glass substrate into a mixed solution of 0.1mol/L NaOH and 0.001mol/L LiOH for corrosion, wherein the corrosion time is 25min, and the temperature of the corrosive liquid is 40 ℃. And taking out the corroded glass substrate, and cleaning the glass substrate with water to obtain the anti-reflection and anti-reflection film layer with the porous structure on the glass substrate.

Example 3

(1) Weighing ethyl orthosilicate, absolute ethyl alcohol and KH550 with a molar ratio of 1:9.4:5, and uniformly mixing and stirring under the action of a magnetic stirrer to obtain a mixed solution A; weighing an acid catalyst (prepared by mixing 1/3 hydrochloric acid with the mass fraction of 30% and 2/3 nitric acid with the mass fraction of 10%) and deionized water with the molar ratio of 0.01:20, and uniformly mixing and stirring under the action of a magnetic stirrer to obtain a mixed solution B; and slowly dripping the mixed solution B into the mixed solution A by using a dropper, continuously stirring the mixed solution A in the dripping process until the mixed solution A and the mixed solution A are completely mixed, continuously stirring for 5 hours, and standing for 1 day to obtain the silica sol.

(2) Weighing 3.6g of polyacrylic acid with molecular weight of 2000, dissolving the polyacrylic acid in 20mL of ammonia water, obtaining a mixed solution C after the polyacrylic acid is completely dissolved, adding all the mixed solution C into 300mL of absolute ethyl alcohol, uniformly mixing under magnetic stirring, dropwise adding 0.2mL of ethyl orthosilicate for 15 times by a pipette every 20min, continuously stirring for 5 hours after completion, obtaining hollow silica particles with average particle size of 60nm and average shell thickness of 12nm, and respectively centrifugally washing the hollow silica particles for 3 times by using deionized water and absolute ethyl alcohol for later use.

(3) Weighing silica sol, hollow silica particles and Disperbyk-2050 in a mass ratio of 1:0.2:0.02, and mixing and stirring for 1 hour under the action of a magnetic stirrer to obtain a coating solution.

(5) In a hundred-grade dust-free operation room, 3g of coating solution is coated on the surface of the cleaned glass by a wire bar coater, the glass is kept stand for 20 minutes, after a film layer on the surface of the glass substrate is leveled, the film layer is dried by an infrared lamp with the power of 1.5kw, the surface temperature of the glass is controlled at 70 ℃, and the glass substrate is placed in an oven with the temperature of 220 ℃ for curing for 10 minutes after drying.

(6) And taking out the glass substrate from the oven after the temperature of the glass substrate is reduced to room temperature, putting the glass substrate into a mixed solution of 0.2mol/L NaOH and 0.001mol/L LiOH for corrosion, wherein the corrosion time is 25min, and the temperature of the corrosive liquid is 30 ℃. And taking out the corroded glass substrate, and cleaning the glass substrate with water to obtain the anti-reflection and anti-reflection film layer with the porous structure on the glass substrate.

Example 4

(1) Weighing ethyl orthosilicate, absolute ethyl alcohol and KH560 in a molar ratio of 1:14.6:1.5, and uniformly mixing and stirring under the action of a magnetic stirrer to obtain a mixed solution A; weighing hydrochloric acid and deionized water with the mass fraction of 30% and the molar ratio of 0.05:13, and uniformly mixing and stirring under the action of a magnetic stirrer to obtain a mixed solution B; and slowly dripping the mixed solution B into the mixed solution A by using a dropper, continuously stirring the mixed solution A in the dripping process until the mixed solution A and the mixed solution A are completely mixed, continuously stirring for 5 hours, and standing for 1 day to obtain the silica sol.

(2) Weighing 3.6g of polyacrylic acid with molecular weight of 2000, dissolving in 20mL of ammonia water, obtaining a mixed solution C after the polyacrylic acid is completely dissolved, adding the mixed solution C into 300mL of absolute ethyl alcohol, uniformly stirring and mixing under magnetic stirring, slowly dropwise adding 0.2mL of ethyl orthosilicate by using a rubber head dropper every 20min, continuing for 5 hours to obtain hollow silica particles with average particle size of 60nm and average shell thickness of 12nm, and respectively centrifugally washing the hollow silica particles for 3 times by using deionized water and absolute ethyl alcohol for later use.

(3) Weighing silica sol, hollow silica particles and Disperbyk-171 in a mass ratio of 1:0.3:0.02, and mixing and stirring for 1 hour under the action of a magnetic stirrer to obtain a coating solution.

(4) A glass substrate with the size of 300mm multiplied by 3mm (length multiplied by width multiplied by thickness) is taken, the surface of the glass is polished by polishing solution prepared by cerium oxide, then the glass is washed clean by deionized water, and then the glass substrate is cleaned by acetone and absolute ethyl alcohol for 10 minutes in an ultrasonic mode in sequence, and then the glass substrate is taken out and is placed into a 60 ℃ oven to be dried for later use.

(5) In a hundred-grade dust-free operation room, 30g of coating solution is coated on the surface of the cleaned glass by a wire bar coater, the glass is kept stand for 20 minutes, after a film layer on the surface of the glass substrate is leveled, the film layer is dried by an infrared lamp with the power of 1.5kw, the surface temperature of the glass is controlled at 70 ℃, and the glass substrate is placed in an oven with the temperature of 200 ℃ for curing for 30 minutes after drying.

Comparative example 1

The steps and values of comparative example 1 are the same as those of example 1, except that step (6) is eliminated and the film layer of the glass substrate is etched.

Examples Performance testing

And testing the thickness of the prepared anti-reflection film layer by using a step instrument, measuring the refractive index of the film layer by using an ellipsometer, calculating the porosity of the film layer according to the measured refractive index, and measuring the reflectivity of the surface of the glass substrate in a visible light range of 380-780 nm by using an ultraviolet-visible spectrophotometer.

Table 1 shows the thickness, refractive index, porosity and reflectivity of the antireflective coating layers of examples 1, 2, 3, 4 and 5.

The results show that: by comparing the example 1 with the comparative example 1, it can be seen visually that after the surface of the antireflection film layer is corroded, the refractive index and the porosity of the antireflection film layer can be greatly improved, the refractive index of the antireflection film prepared by the method can reach 1.25, the porosity can reach 57.1%, the average reflectivity of the glass surface coated with the antireflection film in a 380-780 nm visible light wave band is reduced to be below 2%, even to be 0.8%, and compared with the reflectivity of 4.3% of the antireflection film layer which is not corroded, the surface reflectivity of the glass substrate is obviously improved, so that the higher antireflection requirements of automobile glass, locomotive glass, aircraft glass and the like can be met.

The foregoing detailed description of the preferred embodiments of the invention has been presented. It should be understood that numerous modifications and variations could be devised by those skilled in the art in light of the present teachings without departing from the inventive concepts. The technical solutions available to a person skilled in the art through logical analysis, reasoning or limited experiments based on the prior art according to the concept of the present invention are all within the scope of protection defined by the claims.

Claims

1. A preparation method of an anti-reflection film layer is characterized by comprising the following steps:

C. slowly dripping the mixed solution B into the mixed solution A, keeping the mixed solution A in a continuously stirred state until the dripping of the mixed solution B is finished, and standing to obtain silica sol;

D. mixing and stirring silica sol, hollow silica particles and a dispersing agent in a mass ratio of 1 (0.01-0.5) to 0.01-0.5 to prepare a coating solution;

F. coating the coating solution on a glass substrate by adopting a roll coating method, drying the surface of the glass substrate for 10-40 min under the condition of controlling the surface temperature of the glass substrate to be 50-70 ℃ after a film layer on the surface of the glass substrate is leveled, and curing for 10-60 min under the condition of 180-220 ℃, so as to form a film layer on the surface of the glass substrate;

G. placing the glass substrate in an alkaline solution for corrosion for 20-30 min at the corrosion temperature of 20-40 ℃, forming a concave-convex suede surface on the surface of the corroded film layer, then cleaning the surface with deionized water, and drying to obtain the coated glass with the anti-reflection film layer porosity of 25.7-57.1%.

2. The method for preparing an antireflection film layer according to claim 1, wherein the silicon alkoxide is selected from one or a mixture of two of ethyl orthosilicate and methyl orthosilicate.

3. The method for preparing an antireflection film layer according to claim 1, wherein the alcohol solvent is one or more selected from methanol, ethanol, propanol and butanol.

4. The method of claim 1, wherein the silane coupling agent is selected from the group consisting of KH550, KH560 and KH 570.

5. The method of claim 1, wherein the acid catalyst is selected from one or a mixture of hydrochloric acid and nitric acid.

6. The method for preparing an antireflective film layer according to claim 1, wherein the dispersant is one selected from Disperbyk2050, Disperbyk185, Disperbyk171 and Disperbyk 174.

7. The method for preparing an antireflection film layer according to claim 1, wherein the alkaline solution is one or a mixture of any two of a NaOH solution, a KOH solution and a LiOH solution.

8. The method of claim 1, wherein the hollow silica particles are selected from one or more of the following: spherical hollow silica particles, hemispherical hollow silica particles, ellipsoidal hollow silica particles, and columnar hollow silica particles.

9. The method for preparing an antireflection film layer according to claim 1 or 7, wherein the concentration of the alkaline solution is 0.01mol/L to 0.5 mol/L.

10. An antireflection film layer obtained by the production method according to any one of claims 1 to 9, characterized in that: the porosity of the antireflection film layer is 25.7% -57.1%, and the thickness of the antireflection film layer is 100-200 nm.