阅读说明：本技术 一种防眩光涂膜ag玻璃的制备方法 (Preparation method of anti-glare coated AG glass ) 是由 凌卫平 倪宏达 高鑫 张凯 于 2020-07-23 设计创作，主要内容包括：本发明公开了一种防眩光涂膜AG玻璃的制备方法,本发明属于减反射玻璃技术领域,本发明通过等离子聚合反应在玻璃表面形成不溶不熔的高分子涂膜,制备的防眩光涂膜AG玻璃具有高透光率,高分子镀膜具有良好的强度,不溶不熔,表面硬度高,具有良好的耐磨性能,且折射率下,能使玻璃的透光率得到显著提高,且具有自清洁防静电功能,具有高强度、高热稳定性、耐高温急变、高化学稳定性、耐老化、耐酸碱侵蚀,在恶劣使用环境中经久耐用,平整度好,使用寿命长。(The invention discloses a preparation method of anti-glare film-coated AG glass, which belongs to the technical field of anti-reflection glass.)

1. The preparation method of the anti-glare coated AG glass is characterized by comprising the following steps of:

step one, cleaning treatment of a glass substrate:

soaking the surface of the glass substrate in a cleaning solution, ultrasonically cleaning the surface of the glass substrate with acetone, washing the surface of the glass substrate with deionized water, ultrasonically cleaning the surface of the glass substrate with ethanol, washing the surface of the glass substrate with deionized water, and drying the surface of the glass substrate for 30-40 min at the temperature of 60-65 ℃ for later use;

step two, vacuum evaporation of barium fluoride:

selecting the evaporation source as barium fluoride in the vacuum degree of 1.5X 10^-3~2.5×10^-3Pa, the glass substrate temperature is 250-300 ℃, the glass surface is vacuum evaporated and then vacuum annealed under the substrate distance of 5-15 cm, and the vacuum degree is 1 multiplied by 10^-2~2×10^-2Pa, annealing at the annealing temperature of 100-150 ℃, annealing for 2-4 h, and cooling at the temperature of 20 ℃/min to obtain the evaporated barium fluoride coated glass;

and step three, placing the evaporated barium fluoride coated glass obtained in the step two on a table base of a grounding electrode of a reaction chamber in a Plasma Enhanced Chemical Vapor Deposition (PECVD) and taking the evaporated barium fluoride coated glass as a substrate, wherein the distance between the substrates is 5-6 cm, the glow discharge frequency is 13.56MHz, when the vacuum degree of an inner chamber reaches 0.1-0.2 Pa, activating the surface of a sample by using argon plasma for 2-5 min, then inputting thiophene monomer steam into the inner chamber by using argon as a carrier, maintaining the reaction pressure of the inner chamber at 10-15 Pa, carrying out glow discharge initiated polymerization reaction for 10-20 min, carrying out heat preservation at 50-65 ℃ for 5-10 min, taking out, sending the glass into a drying oven at 100-110 ℃, carrying out polymerization reaction for 10-12 h, and cooling to obtain the anti-glare coated.

2. The method for preparing anti-glare coated AG glass according to claim 1, wherein the thiophene monomer of the third step is one of 3, 4-ethylenedioxythiophene, thiophene and 3-hexylthiophene.

3. The method for preparing anti-glare film-coated AG glass according to claim 1, wherein the cleaning solution of the first step is a mixture of alcohol, surfactant and alkane; the alcohol is selected from one or more of propylene glycol, n-butanol, n-amyl alcohol, isopropanol, n-hexyl alcohol, ethanol and n-octyl alcohol; the alkane is selected from one or more of n-pentane, n-hexane, n-heptane, benzene, toluene, ethylbenzene and xylene; the surfactant is selected from one or more of diphenylamine sodium sulfonate, sodium polypropylene sulfonate, poly (chlorinated diallyl dimethyl ammonium), polyvinylpyrrolidone and polyethylene glycol, wherein the molar ratio of the alcohol to the alkane to the surfactant is 1-10: 1-10: 0.1 to 0.5.

4. The method for preparing anti-glare coated AG glass according to claim 1, wherein the average thickness of the barium fluoride coating layer evaporated in vacuum in the second step is 100-150 nm.

5. The method for preparing the anti-glare coated AG glass according to claim 1, wherein the soaking time of the cleaning solution in the first step is 20-30 min.

6. The method for preparing the anti-glare coated AG glass according to claim 1, wherein the steam flow of the thiophene monomer in the third step is 3-4 mL/min.

7. The method for preparing the anti-glare film-coated AG glass according to claim 1, wherein the flow rate of argon in the third step is 40-45 mL/min.

Technical Field

The invention belongs to the technical field of antireflection glass, and particularly relates to a preparation method of anti-glare coating AG glass.

Background

The scattering effect of the rough surface is utilized to convert a large amount of incident light into diffuse reflection light, the diffuse reflection light does not bring obvious change to the transmittance, and the glass produced by the fine roughening is called AG glass. The glass is coated with one or more layers of transparent metal films or metal oxide films which can absorb heat. Antireflection glass, also called anti-reflection glass, AG glass for short, has a refractive index of about 1.52, and is also called "invisible glass" because the surface of the glass is coated with a transparent film having a small refractive index, so that the reflected light from the upper and lower surfaces of the film interferes with each other to maximize the transmittance, and the transmission image is clear as if the glass is invisible. The antireflection glass is also called as "non-reflection glass". Glass capable of reducing reflected light. The surface of the glass is coated with a film with a refractive index smaller than that of the glass so as to reduce the reflection amount of light. In the prior art, a layer of magnesium fluoride film is coated by a vacuum evaporation coating method, the reflectivity of magnesium fluoride is low, the transmittance of magnesium fluoride is less changed along with the temperature change, the magnesium fluoride film can be used as protective glass used for exhibition windows, pictures, electronic instruments and the like, infrared window glass and the like, and the existing antireflection glass on the market mainly comprises the following components: the vacuum sputtering coated glass, the gel-sol coated glass and the special ultra-white cloth grain glass for packaging the solar cell can generate diffuse reflection even under the strong light condition, further reduce the reflection of the screen, improve the visibility and the brightness of a display picture, enable the image to be clearer and the color to be more saturated, thereby generating good visual effect, creating a clear and transparent visual space and enabling an observer to experience better visual enjoyment. With the advance of urbanization, high-rise buildings built in various places increasingly adopt glass curtain walls as decorations, and the problem of light pollution caused by the glass curtain walls is becoming serious. On the one hand, light pollution is a fierce in making an accident, under the blazing of burning sun, a traffic signal lamp and a running vehicle can pass through a building glass curtain wall beside a passage or at a traffic intersection to generate reflected light, and the reflected light can cause sudden temporary blindness and visual illusion to a driver, thereby seriously harming pedestrians and driving safety. On the other hand, the glass curtain wall near the residential area can reflect light to surrounding buildings, and certain troubles are inevitably brought to residents living nearby. Light pollution caused by reflected light is difficult to eliminate or reduce by means of decomposition, conversion or dilution and the like other pollution, so that the antireflection glass becomes an ideal material for high-grade building glass. The polythiophene synthesizing process includes mainly chemical oxidation polymerization, electrochemical polymerization, enzyme catalytic oxidation and coupling polymerization with transition metal element as medium. In daily life, people have experience of being attacked by glare, wherein part of the experience is from a glare light source, and part of the experience is from glare reflection. For example, when a computer is operated, due to the existence of the glass show window, the liquid crystal display screen and the liquid crystal touch screen cannot clearly see the displayed content due to reflection. The glass show window made of the antireflection glass can effectively solve the problem of glare pollution. The antireflection glass has the advantages that the surface light reflectivity of the antireflection glass is reduced and the perspective performance is enhanced by adopting a spraying method, a sol-gel immersion plating method, a magnetron sputtering method, a vacuum evaporation method or an acid etching method, but the magnetron sputtering method has relatively complex process and high requirements on environment and equipment, so the cost is higher, the vacuum evaporation method has relatively complex process and relatively high cost, the antireflection glass is not corrosion-resistant and has poor scratch-resistant performance under severe conditions such as strong light irradiation or outdoor wind, rain and the like, the antireflection glass is easy to wear and shine after being used for a period of time, a coating layer is easy to fall off or change color and lose the antiglare effect, and for example, Chinese patent CN2017109774660 discloses wear-resistant fingerprint-resistant frosted glass and a preparation method; in view of the above problems, a person skilled in the art needs to develop a method for preparing an anti-glare coating AG glass to meet the existing performance requirements and market requirements.

Disclosure of Invention

The invention aims to provide a preparation method of anti-dazzle coated AG glass aiming at the existing problems.

PECVD refers to plasma enhanced chemical vapor deposition. The gas containing film component atoms is locally formed into plasma by means of microwave or radio frequency, etc., and the plasma has strong chemical activity and is easy to react to deposit the desired film on the substrate.

PEDOT is a polymer of 3, 4-ethylenedioxythiophene monomer, and is a thiophene polymer, and the application of PEDOT is limited at present because PEDOT is an insoluble polymer. At present, the processing problem of PEDOT is solved by widely doping water-soluble polyelectrolyte polystyrene sulfonic acid (PSS).

The invention is realized by the following technical scheme:

a preparation method of anti-glare coated AG glass comprises the following steps:

step one, cleaning treatment of a glass substrate:

soaking the surface of the glass substrate in a cleaning solution, ultrasonically cleaning the surface of the glass substrate with acetone, washing the surface of the glass substrate with deionized water, ultrasonically cleaning the surface of the glass substrate with ethanol, washing the surface of the glass substrate with deionized water, and drying the surface of the glass substrate for 30-40 min at the temperature of 60-65 ℃ for later use;

step two, vacuum evaporation of barium fluoride:

selecting the evaporation source as barium fluoride in the vacuum degree of 1.5X 10^-3~2.5×10^-3Pa, the glass substrate temperature is 250-300 ℃, the glass surface is subjected to vacuum evaporation coating at a substrate distance of 5-15 cm, and then vacuum annealing is carried out, wherein the vacuum degree is as follows: 1X 10^-2~2×10^-2Pa, annealing at the annealing temperature of 100-150 ℃, annealing for 2-4 h, and cooling at the temperature of 20 ℃/min to obtain the evaporated barium fluoride coated glass;

and step three, placing the evaporated barium fluoride coated glass obtained in the step two on a table base of a grounding electrode of a reaction chamber in a Plasma Enhanced Chemical Vapor Deposition (PECVD) and taking the evaporated barium fluoride coated glass as a substrate, wherein the distance between the substrates is 5-6 cm, the glow discharge frequency is 13.56MHz, when the vacuum degree of an inner chamber reaches 0.1-0.2 Pa, activating the surface of a sample by using argon plasma for 2-5 min, then inputting thiophene monomer steam into the inner chamber by using argon as a carrier, maintaining the reaction pressure of the inner chamber at 10-15 Pa, carrying out glow discharge initiated polymerization reaction for 10-20 min, carrying out heat preservation at 50-65 ℃ for 5-10 min, taking out, then sending the glass into a baking oven at 100-110 ℃ for carrying out polymerization reaction for 10-12 h, and cooling to obtain the anti-glare film.

Further, the cleaning solution of the first step is a mixture of alcohol, a surfactant and alkane; the alcohol is selected from one or more of propylene glycol, n-butanol, n-hexanol, n-pentanol, isopropanol, ethanol and n-octanol; the alkane is selected from one or more of n-pentane, benzene, toluene, n-hexane, n-heptane, ethylbenzene and xylene; the surfactant is one or more selected from diphenylamine sodium sulfonate, polyvinylpyrrolidone, polyethylene glycol, sodium polypropylene sulfonate and poly (chlorinated diallyl dimethyl ammonium), wherein the molar ratio of the alcohol to the alkane to the surfactant is 1-10: 1-10: 0.1 to 0.5.

Furthermore, the thiophene monomer in the third step is one of thiophene, 3-hexylthiophene and 3, 4-ethylenedioxythiophene.

Further, the steam flow of the thiophene monomer in the third step is 3-4 mL/min.

Further, the flow of the argon gas in the third step is 40-45 mL/min.

Furthermore, the average thickness of the vacuum evaporation barium fluoride coating is 100-150 nm.

Further, the time for soaking treatment of the cleaning solution is 20-30 min.

The invention has the beneficial effects that:

the invention adopts a plasma polymerization mode to initiate thiophene monomer polymerization, forms an insoluble and infusible polymer film layer on a barium fluoride coating to realize double-layer coating, thereby achieving the technical effects of permeability increasing and antireflection, realizes oriented compounding on the evaporated barium fluoride coating by utilizing PECVD after the barium fluoride is evaporated in vacuum, greatly improves the tolerance and the strength of the whole film layer, realizes the protection of the polymer film layer on the barium fluoride low-refraction coating on the premise of not using a doping agent and not increasing the cost of the original technical equipment, simultaneously has lower refractive index and good permeability increasing performance, and is also used as the permeability increasing film layer, and the self antistatic performance ensures that the film layer is easy to clean and not easy to adsorb dust, has good corrosion resistance and scratch resistance under the harsh conditions of rain and the like, and is not easy to fall off or change color, the plasma polymerization is adopted as a new polymerization method, the difference with other traditional polymerization modes is obvious, the plasma contains various active particles, the monomer can be initiated to carry out polymerization reaction, the advantages of short initiation time, high initiation efficiency and almost no introduction of any impurity in the initiation process are achieved, and the ultrathin, compact, firm, highly uniform, pinhole-free, high crosslinking density and corrosion-resistant protective anti-reflection film layer can be formed.

Compared with the prior art, the invention has the following advantages:

the invention discloses a preparation method of anti-glare AG glass, which is characterized in that the AG glass adopts a magnesium fluoride film, is only limited to the anti-reflection use of glass with a refractive index of more than 1.6, can not greatly meet the anti-reflection requirement of the glass with a lower refractive index, and an inorganic film layer comprising magnesium fluoride has poor anti-corrosion and anti-scratch performance under the harsh conditions of outdoor wind, rain and the like, is easy to generate abrasion and shine after being used for a period of time, a film coating layer is easy to fall off or discolor, and loses the anti-glare effect, while when the glass with the inorganic film layer is coated and protected by adopting plastic films, coatings and the like, the anti-reflection performance is poor and the whole thickness is increased. The preparation method is simple and convenient, the cost is low, a dopant or a solvent or a dispersant of polythiophene and derivatives thereof is not used, the direct forming is simple and convenient, the prepared anti-glare film-coated AG glass has high light transmittance, the high-molecular film coating has good strength, the light transmittance of the glass can be obviously improved, the glass has a self-cleaning and anti-static function, and has high strength, high thermal stability, high temperature and shock resistance, high chemical stability, aging resistance, acid and alkali erosion resistance, durability in severe use environment, good flatness and long service life.

Detailed Description

The invention is illustrated by the following specific examples, which are not intended to be limiting.