CN111960691A - Coated glass with surface self-cleaning function - Google Patents

Abstract

The invention discloses coated glass with a self-cleaning surface, which comprises a glass substrate, wherein the glass substrate can be any conventional transparent glass substrate in the field of solar photovoltaic glass, and is preferably an ultrawhite rolled glass substrate; one side of the glass substrate is coated with a layer of antireflection film, and the antireflection film is a silicon dioxide film layer, so that the transmittance of the coated glass can be effectively improved; the self-cleaning coating is a super-hydrophobic coating, can effectively improve the self-cleaning performance of the coated glass, and has higher practicability. The technical scheme has the advantages of reasonable process design and simple operation, not only effectively improves the bonding performance between the self-cleaning coating and the antireflection film and prolongs the service life of the coated glass, but also effectively improves the super-hydrophobic performance and the self-cleaning performance of the coated glass by modifying the silicon dioxide gel to form a super-hydrophobic plane on the surface of the coated glass.

Description

A coated glass with self-cleaning surface

technical field

The invention relates to the technical field of coated glass, in particular to a coated glass with surface self-cleaning.

Background technique

Coated glass, also known as reflective glass. Coated glass is to coat one or more layers of metal, alloy or metal compound films on the surface of the glass to change the optical properties of the glass to meet certain specific requirements. Coated glass can be divided into the following categories according to the different characteristics of the product: heat-reflective glass, low-emissivity glass (Low-E), conductive film glass, etc.

Heat reflective glass is generally coated with one or more layers of metal or its compounds such as chromium, titanium or stainless steel on the surface of the glass to make the product rich in color, with appropriate transmittance for visible light and higher for infrared. Reflectivity, high absorption rate of ultraviolet rays, therefore, also known as solar control glass, mainly used in buildings and glass curtain walls; low-emissivity glass is coated on the glass surface with multiple layers of metals such as silver, copper or tin or their compounds. It has high transmittance to visible light, high reflectivity to infrared rays, and good thermal insulation performance. It is mainly used in buildings and vehicles such as automobiles and ships. They are all made into insulating glass; conductive film glass is coated with conductive films such as indium tin oxide on the surface of the glass, which can be used for heating, defrosting, defogging, and liquid crystal displays.

Nowadays, there is still a kind of glass that is highly concerned about self-cleaning glass, that is, the self-cleaning effect is achieved by super-hydrophobic surface or super-hydrophilic surface, but the self-cleaning glass on the market today has a short service life, and the self-cleaning coating on the glass surface The contact between the layer and the anti-reflection film is not close, and the adhesion is poor, which brings us great inconvenience.

In view of the above situation, we designed a coated glass with surface self-cleaning and its preparation method. This is one of the problems we need to solve urgently.

SUMMARY OF THE INVENTION

The purpose of the present invention is to provide a coated glass with surface self-cleaning and a preparation method thereof, so as to solve the problems in the prior art.

To achieve the above object, the present invention provides the following technical solutions:

A coated glass with surface self-cleaning, the coated glass includes a glass substrate, an anti-reflection film and a self-cleaning coating, the anti-reflection film is coated on one side surface of the glass substrate, and the self-cleaning coating is coated On the anti-reflection film; the thickness of the anti-reflection film is 50-100 nm, and the thickness of the self-cleaning coating is 100-200 nm.

The invention discloses a coated glass with surface self-cleaning and a preparation method thereof, wherein the coated glass includes a glass substrate, and the glass substrate can be any glass substrate conventionally used for light transmission in the field of solar photovoltaic glass, preferably an ultra-white glass substrate. Rolled glass substrate; one side of the glass substrate is coated with an anti-reflection film, which is a silicon dioxide film layer, which can effectively improve the transparency of the coated glass; the anti-reflection film is coated with a layer of self-cleaning The cleaning coating is a super-hydrophobic coating, which can effectively improve the self-cleaning performance of the coated glass and has high practicability.

Preferably, the self-cleaning coating includes an adhesive layer and a modified silica gel layer, the adhesive layer is coated on the anti-reflection film, and the modified silica gel layer is coated on the anti-reflection film. on the adhesive layer; the thickness of the adhesive layer is 50-100 nm, and the thickness of the modified silica gel layer is 50-100 nm.

The self-cleaning coating in this technical solution includes an adhesive layer and a modified silica gel layer. It is well known that when coating glass is prepared, a layer of anti-reflection coating is generally applied on the surface of the coated glass, and then the self-cleaning coating on the surface is coated. Cleaning coating, however, in this technical solution, the self-cleaning coating is selected as a super-hydrophobic coating. When the super-hydrophobic coating is applied, the adhesion between the anti-reflection coating and the anti-reflection coating is poor; after the coated glass is used for a period of time, the The super-hydrophobic coating is easy to fall off, thereby reducing the self-cleaning performance of the coated glass; in view of this problem, this technical solution designs the self-cleaning coating as an adhesive layer and a modified silica gel layer combined with each other, and the adhesive layer is first It is coated on the surface of the glass substrate, and then the modified silica gel layer is coated on the top of the bonding layer, and the modified silica gel layer is used as a super-hydrophobic coating. The connection bridge between the silica gel layer and the glass substrate improves the connection between the self-cleaning coating and the glass substrate more tightly.

Preferably, each raw material component of the modified silica gel layer includes: by weight, 15-25 parts of tetraethyl silicate, 10-20 parts of ethanol, 20-40 parts of ammonia water, heptadecafluorodecane 5-15 parts of trimethoxysilane and 3-8 parts of crosslinking agent.

The raw materials for the modified silica gel layer in this technical solution include tetraethyl silicate, ethanol, ammonia water, heptadecafluorodecyltrimethoxysilane, and cross-linking agent, wherein tetraethyl silicate, ethanol and ammonia water can be Silica gel is prepared by sol-gel method to form a superhydrophobic surface, and then fluorosilane and cross-linking agent are added for modification, so that the silica gel is hydrophobized and modified, which will build the surface rough structure and reduce the coating. The surface energy is perfectly combined to further improve the superhydrophobicity of the modified silica gel layer.

Preferably, each raw material component of the adhesive layer includes: by weight, 8-16 parts of methanol, 15-30 parts of vinyl acetate, 5-10 parts of sodium hydroxide, 5-12 parts of aluminum sulfate, defoaming 3-5 parts of agent, 3-6 parts of preservative, 2-6 parts of starch.

The raw materials of the adhesive layer in this technical solution include methanol, vinyl acetate, sodium hydroxide, aluminum sulfate, defoaming agent, preservative, and starch; wherein the design of methanol, vinyl acetate, and sodium hydroxide can prepare polyvinyl alcohol , in an alkaline environment of sodium hydroxide, polyvinyl alcohol is generated after vinyl acetate alcoholysis; the reason why polyvinyl alcohol is prepared by alcoholysis of vinyl acetate instead of existing polyvinyl alcohol is that in vinyl acetate In the case of ester alcohol, acetic acid can be produced, and in the environment of sodium hydroxide and acetic acid, the surface of the anti-reflection film will corrode to form a rough surface, which can further improve the bonding force between the adhesive layer and the anti-reflection film, and ensure the stability of the self-cleaning coating. ; At the same time, aluminum sulfate, defoamer, preservative, starch and the generated polyvinyl alcohol can react with each other to form a viscous bonding layer, and realize the tight combination between the modified silica gel layer and the anti-reflection film. .

Preferably, the crosslinking agent is γ-(2,3-glycidoxy)propyltrimethoxysilane.

Preferably, a method for preparing coated glass with surface self-cleaning comprises the following steps:

1) Raw material preparation;

2) coating of anti-reflection film;

3) Coating masking film on the side that is not coated with anti-reflection film;

4) Apply a self-cleaning coating on the anti-reflection film;

a) coating of the adhesive layer;

b) coating of the modified silica gel layer;

5) Remove the mask;

6) End the operation.

More optimally, it includes the following steps:

1) Raw material preparation;

a) Weigh tetraethyl silicate, ethanol, ammonia water, heptadecafluorodecyltrimethoxysilane and γ-(2,3-glycidoxy)propyltrimethoxysilane in proportion for subsequent use;

b) take by weighing methanol, vinyl acetate, sodium hydroxide, aluminum sulfate, defoamer, preservative and starch in proportion, for subsequent use;

c) Cleaning the glass substrate for use;

2) Coating of anti-reflection film: take the glass substrate cleaned in step 1), apply anti-reflection film liquid on the surface of one side of the glass substrate by roller coating method, and cure at low temperature to form an anti-reflection film;

3) Take the glass substrate treated in step 2), coat a layer of photoresist on the side that is not coated with the anti-reflection film, and bake to cure the masking film to form a masking film;

4) Application of self-cleaning coating:

a) Preparation of polyvinyl alcohol:

A. Take the methanol prepared in step 1), put the methanol into a four-necked flask, add sodium hydroxide solution, and turn on the stirrer to stir;

B. Put the vinyl acetate prepared in step 1) into the dropping funnel, slowly dropwise into the four-necked flask in 25-35min, and stir to react to obtain the first material;

b) Application of the adhesive layer:

A. Take the first material after the reaction in step a) and pour it into a beaker, then put the glass substrate treated in step 3) into the beaker, heat it up to 40-50°C, and react;

B. Take the beaker treated in step A, heat it up to 80-90°C, stir at a constant temperature, then put the aluminum sulfate, starch, defoamer and antiseptic prepared in step 1) into the beaker in turn, and cool to room temperature after stirring, At this time, an adhesive layer is formed on the surface of the glass substrate, and then the glass substrate is taken out for use;

c) Coating of the modified silica gel layer:

A. Take the tetraethyl silicate and ethanol prepared in step 1), put them into a beaker, perform magnetic stirring at room temperature, and then take the ammonia water prepared in step 1) and slowly add it dropwise into the beaker during the stirring process. , continue to stir, after stirring, stand for aging to obtain silica gel;

B. Take heptadecafluorodecyltrimethoxysilane and γ-(2,3-glycidoxy)propyltrimethoxysilane prepared in step 1), dilute with ethanol, and then put them into the beaker of step A in turn, Ultrasonic stirring to obtain modified silica gel;

C. Take the glass substrate treated in step a), place it on a glue-slung platform, with the uncoated side facing down, evenly drop the modified silica gel obtained in step B, and drop the glue for 1- 2min, and then placed on a hot plate for 2-4min; repeated slinging 3-5 times, and then placed in an oven for thermosetting to form a modified silica gel layer;

5) Remove the masking film: take the glass substrate processed in step 4), remove the masking film on one side of the glass substrate, and then clean it with deionized water;

6) End the operation.

More optimally, it includes the following steps:

1) Raw material preparation;

a) Weigh tetraethyl silicate, ethanol, ammonia water, heptadecafluorodecyltrimethoxysilane and γ-(2,3-glycidoxy)propyltrimethoxysilane in proportion for subsequent use;

b) take by weighing methanol, vinyl acetate, sodium hydroxide, aluminum sulfate, defoamer, preservative and starch in proportion, for subsequent use;

c) Cleaning the glass substrate for use; in step 1), prepare the raw materials required for subsequent operations, and clean the glass substrate to remove the oil stain on the surface of the glass substrate and keep the surface of the glass substrate dry for subsequent operations;

2) Coating of anti-reflection film: take the cleaned glass substrate in step 1), apply anti-reflection film liquid on the surface of one side of the glass substrate by roll coating method, and cure at low temperature to form an anti-reflection film; in step 2) Coat the anti-reflection film on one side of the glass substrate, and apply it by roller coating method. In practice, it can also be applied by spraying method;

3) Take the glass substrate treated in step 2), coat a layer of photoresist on the side that is not coated with the anti-reflection film, bake to solidify the masking film, and form a masking film; wherein the baking temperature is 95-100°C , the baking time is 15-20min; in step 3), coat the photoresist on the side of the glass substrate that is not coated with the anti-reflection film, and form a masking film after curing. When cleaning the coating, the side of the glass substrate that does not need to be processed is also coated with a self-cleaning coating to ensure the smooth progress of subsequent operations;

4) Application of self-cleaning coating:

a) Preparation of polyvinyl alcohol:

A. Take the methanol prepared in step 1), put the methanol into a four-necked flask equipped with a stirrer, a condenser, a thermometer and a dropping funnel, add sodium hydroxide solution, turn on the stirrer and stir, and the stirring time is 2-5min;

B. Put the vinyl acetate prepared in step 1) into the dropping funnel, slowly drop it into the four-necked flask within 25-35min, and stir for 1.5-2.5h to obtain the first material; step 4) carry out For the coating of self-cleaning coating, firstly, methanol is used as an alcoholysis agent and sodium hydroxide is used as a catalyst to make vinyl acetate alcoholysis in an alkaline environment to generate polyvinyl alcohol;

b) Application of the adhesive layer:

A. Take the first material after the reaction in step a), pour it into a beaker, then put the glass substrate treated in step 3) into the beaker, heat it up to 40-50°C, and react for 15-25min; in step A , After the production of polyvinyl alcohol, sodium hydroxide solution and the generated acetic acid are still left in the four-necked flask. Putting the glass substrate in the residual liquid can form a rough surface on the anti-reflection film of the glass substrate, which is convenient for subsequent coating. When the adhesive layer is applied, the bond between the adhesive layer and the anti-reflection film is more tightly bound;

B. Take the beaker treated in step A, heat it up to 80-90°C, stir at a constant temperature for 8-12min, and then put the aluminum sulfate, starch, defoamer and preservative prepared in step 1) into the beaker in turn, and stir for 3- 5min, cooled to room temperature after stirring, at this time an adhesive layer was formed on the surface of the glass substrate, and then the glass substrate was taken out for use; in step B, raw materials such as aluminum sulfate were added to the beaker, and the produced polyvinyl alcohol was used to react with each raw material , a bonding layer will be formed on the surface of the anti-reflection film;

c) Coating of the modified silica gel layer:

A. Take the tetraethyl silicate and ethanol prepared in step 1), put them into a beaker, perform magnetic stirring at room temperature, and then take the ammonia water prepared in step 1) and slowly add it dropwise into the beaker during the stirring process. , continue to stir for 250-260min; stand for aging for 10-12h to obtain silica gel;

B. Take heptadecafluorodecyltrimethoxysilane and γ-(2,3-glycidoxy)propyltrimethoxysilane prepared in step 1), dilute with ethanol, and then put them into the beaker of step A in turn, Ultrasonic stirring is performed for 1-2 h to obtain modified silica gel; in step B, the preparation of modified silica gel is performed;

C. Take the glass substrate treated in step a), place it on a glue-slung platform, with the uncoated side facing down, evenly drop the modified silica gel obtained in step B, and drop the glue for 1- 2min, the rotation speed is 1400-1600rpm; then it is placed on a hot plate for 2-4min, and the hot plate temperature is 90-110°C; the glue is repeated 3-5 times, and then placed in an oven for thermosetting to form modified silica Gel layer; wherein the thermosetting temperature is 90-100° C., and the thermosetting time is 30-40min; in step C, the prepared modified silica gel is uniformly coated on the adhesive layer by means of spin coating , the agglomerated silica particles will form a multi-layer micro-nano hole structure. When the water droplets contact the surface of the coated glass, this multi-layer hole structure can form an air film on the surface and reduce the contact between the droplets and the coated glass surface. area, so as to achieve the super-hydrophobic performance of the coated glass;

5) Remove the masking film: take the glass substrate processed in step 4), remove the masking film on one side of the glass substrate, and then wash it with deionized water for 2-4 times; remove the masking film in step 5);

6) End the operation.

Preferably, in the step 2), the temperature during low temperature curing is 280-300° C., and the curing time is 2-5 min.

Preferably, in step c) of the step 1), when cleaning the glass substrate, take the cut glass substrate, soak it in a sodium hydroxide solution for 20-30 minutes, and then rinse it with deionized water. Blow dry with nitrogen.

Compared with the prior art, the beneficial effects of the present invention are:

During the operation of the present invention, firstly prepare the raw materials, and clean the glass substrate to remove the oil stains on the surface of the glass substrate and keep the surface of the glass substrate dry; then coat the anti-reflection film on one side of the glass substrate, and coat the other side with masking film, the masking film can play a protective role to avoid that when the self-cleaning coating is applied, the side of the glass substrate that does not need to be processed is also coated with the self-cleaning coating; then by forming a rough surface on the anti-reflection film while generating The adhesive layer ensures that the adhesive layer can be smoothly and closely combined with the anti-reflection film; then by preparing modified silica gel, the modified silica gel is coated on the adhesive layer to form modified dioxide Silica gel layer, modified silica gel layer, as a superhydrophobic surface, can effectively improve the superhydrophobicity and self-cleaning properties of the coated glass.

The technical solution discloses a coated glass with surface self-cleaning and a preparation method thereof. The process design is reasonable and the operation is simple, which not only effectively improves the bonding performance between the self-cleaning coating and the anti-reflection film, but also improves the service life of the coated glass. At the same time, by modifying the silica gel, a superhydrophobic plane is formed on the surface of the coated glass, which effectively improves the superhydrophobicity and self-cleaning performance of the coated glass.

Detailed ways

The technical solutions in the embodiments of the present invention will be described clearly and completely below. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.

Example 1:

Step S1: raw material preparation; weigh tetraethyl silicate, ethanol, ammonia water, heptadecafluorodecyltrimethoxysilane and γ-(2,3-glycidoxy)propyltrimethoxysilane in proportion, For standby; Weigh methanol, vinyl acetate, sodium hydroxide, aluminum sulfate, defoamer, preservative and starch in proportion for standby;

Step S2: cleaning the glass substrate, when cleaning the glass substrate, take the cut glass substrate, soak it in a sodium hydroxide solution for 20 minutes, rinse it with deionized water, and dry it with nitrogen for use;

Step S3: coating of anti-reflection film: take the cleaned glass substrate, apply anti-reflection film liquid on the surface of one side of the glass substrate by roll coating method, and cure at low temperature to form an anti-reflection film; the temperature during low-temperature curing is 280 ℃, the curing time is 5min;

Step S4: take the processed glass substrate, coat a layer of photoresist on the side that is not coated with the anti-reflection film, bake to cure the masking film, and form a masking film; wherein the baking temperature is 95° C., and the baking time is is 20min;

Step S5: Application of Self-Cleaning Coating:

Step S51: Preparation of polyvinyl alcohol, take the prepared methanol, put the methanol into a four-necked flask equipped with a stirrer, a condenser, a thermometer and a dropping funnel, add sodium hydroxide solution, turn on the stirrer and stir, and the stirring time is: 2min; then put the prepared vinyl acetate into the dropping funnel, slowly add it dropwise to the four-necked flask within 25min, and stir and react for 1.5h to obtain the first material;

Step S52: Coating of the adhesive layer: take the first material after the reaction is completed, pour it into a beaker, then put the glass substrate treated in step 3) into the beaker, heat it up to 40°C, and react for 25 minutes; the beaker is heated The temperature was raised to 80°C, stirred at a constant temperature for 12 minutes, then put the prepared aluminum sulfate, starch, defoamer, and antiseptic into the beaker in turn, stirred for 3 minutes, and cooled to room temperature after stirring. At this time, a bonding layer was formed on the surface of the glass substrate, and then Take out the glass substrate and set aside;

Step S6: Coating of the modified silica gel layer: Take the prepared tetraethyl silicate and ethanol, put them into a beaker, perform magnetic stirring at room temperature, and then take the prepared ammonia water, and slowly add it dropwise to the beaker during the stirring process , after the dropwise addition of ammonia water, continue to stir for 250 min; stand for aging for 10 h to obtain silica gel; take the prepared heptadecafluorodecyltrimethoxysilane and γ-(2,3-glycidoxyloxy) ) propyltrimethoxysilane, diluted with ethanol, then put into a beaker in turn, and ultrasonically stirred for 1 h to obtain modified silica gel;

Take the glass substrate processed in step S5, place it on a glue-spinning platform, with the uncoated side facing down, drop the modified silica gel evenly, spin the glue for 1 min, and set the rotating speed to 1400 rpm; The plate was heated for 2 minutes, and the temperature of the hot plate was 110 °C; the glue was repeatedly thrown for 3 times, and then placed in an oven for thermosetting to form a modified silica gel layer; the thermosetting temperature was 90 °C, and the thermosetting time was 40min;

Step S7: removing the masking film: taking the processed glass substrate, removing the masking film on one side of the glass substrate, and then washing with deionized water twice; the operation is ended.

In this embodiment, the thickness of the anti-reflection film is 50 nm, the thickness of the self-cleaning coating is 100 nm; the thickness of the adhesive layer is 50 nm, and the thickness of the modified silica gel layer is 50 nm .

The raw material components of the modified silica gel layer include: by weight, 15 parts of tetraethyl silicate, 10 parts of ethanol, 20 parts of ammonia water, 5 parts of heptadecafluorodecyltrimethoxysilane, 3 parts of joint agent; each raw material component of the adhesive layer includes: by weight, 8 parts of methanol, 15 parts of vinyl acetate, 5 parts of sodium hydroxide, 5 parts of aluminum sulfate, 3 parts of defoamer, 3 parts of preservatives parts, starch 2 parts; the crosslinking agent is γ-(2,3-glycidoxy)propyltrimethoxysilane.

Example 2:

Step S1: raw material preparation; weigh tetraethyl silicate, ethanol, ammonia water, heptadecafluorodecyltrimethoxysilane and γ-(2,3-glycidoxy)propyltrimethoxysilane in proportion, For standby; Weigh methanol, vinyl acetate, sodium hydroxide, aluminum sulfate, defoamer, preservative and starch in proportion for standby;

Step S2: cleaning the glass substrate, when cleaning the glass substrate, take the cut glass substrate, soak it in a sodium hydroxide solution for 25 minutes, rinse it with deionized water, and dry it with nitrogen for use;

Step S3: coating of anti-reflection film: take the cleaned glass substrate, apply anti-reflection film liquid on the surface of one side of the glass substrate by roller coating method, and cure at low temperature to form an anti-reflection film; the temperature during low-temperature curing is 290 ℃, the curing time is 4min;

Step S4: taking the processed glass substrate, coating a layer of photoresist on the side not coated with the anti-reflection film, and baking the mask to cure the mask to form a mask; wherein the baking temperature is 98°C, and the baking time is 98°C. is 18min;

Step S5: Application of Self-Cleaning Coating:

Step S51: Preparation of polyvinyl alcohol, take the prepared methanol, put the methanol into a four-necked flask equipped with a stirrer, a condenser, a thermometer and a dropping funnel, add sodium hydroxide solution, turn on the stirrer and stir, and the stirring time is: 4min; then put the prepared vinyl acetate into the dropping funnel, slowly add it dropwise to the four-necked flask within 30min, stir and react for 2h to obtain the first material;

Step S52: Coating of the adhesive layer: take the first material after the reaction is completed, pour it into a beaker, then put the glass substrate treated in step 3) into the beaker, heat it to 45°C, and react for 20 minutes; the beaker is heated The temperature was raised to 85 °C, stirred at a constant temperature for 10 minutes, and then the prepared aluminum sulfate, starch, defoaming agent, and antiseptic were put into the beaker in turn, stirred for 4 minutes, and cooled to room temperature after stirring. At this time, a bonding layer was formed on the surface of the glass substrate, and then Take out the glass substrate and set aside;

Step S6: Coating of the modified silica gel layer: Take the prepared tetraethyl silicate and ethanol, put them into a beaker, perform magnetic stirring at room temperature, and then take the prepared ammonia water, and slowly add it dropwise to the beaker during the stirring process , after the dropwise addition of ammonia water, continue to stir for 255 min; stand for aging for 11 h to obtain silica gel; take the prepared heptadecafluorodecyltrimethoxysilane and γ-(2,3-glycidoxyloxy) ) propyltrimethoxysilane, diluted with ethanol, then put into a beaker in turn, and ultrasonically stirred for 1.5h to obtain modified silica gel;

Take the glass substrate processed in step S5, place it on the glue-spinning platform, with the uncoated side facing down, add the modified silica gel dropwise evenly, spin the glue for 1.5 min, and set the rotating speed to 1500 rpm; Heating on a hot plate for 3 minutes, the temperature of the hot plate is 100 ℃; repeat the slinging 4 times, and then put it into an oven for thermosetting to form a modified silica gel layer; the thermosetting temperature is 95 ℃, and the thermosetting time is 35min ;

Step S7: removing the masking film: taking the processed glass substrate, removing the masking film on one side of the glass substrate, and then washing with deionized water for three times; the operation is ended.

In this embodiment, the thickness of the anti-reflection film is 80 nm, the thickness of the self-cleaning coating is 160 nm; the thickness of the adhesive layer is 80 nm, and the thickness of the modified silica gel layer is 80 nm .

The raw material components of the modified silica gel layer include: by weight, 20 parts of tetraethyl silicate, 15 parts of ethanol, 30 parts of ammonia water, 10 parts of heptadecafluorodecyltrimethoxysilane, 5 parts of the joint agent; the raw material components of the adhesive layer include: by weight, 12 parts of methanol, 24 parts of vinyl acetate, 8 parts of sodium hydroxide, 9 parts of aluminum sulfate, 4 parts of defoamer, 4 parts of preservatives parts, starch 4 parts; the crosslinking agent is γ-(2,3-glycidoxy)propyltrimethoxysilane.

Example 3:

Step S1: raw material preparation; weigh tetraethyl silicate, ethanol, ammonia water, heptadecafluorodecyltrimethoxysilane and γ-(2,3-glycidoxy)propyltrimethoxysilane in proportion, For standby; Weigh methanol, vinyl acetate, sodium hydroxide, aluminum sulfate, defoamer, preservative and starch in proportion for standby;

Step S2: cleaning the glass substrate, when cleaning the glass substrate, take the cut glass substrate, soak it in a sodium hydroxide solution for 30 minutes, rinse with deionized water, and dry it with nitrogen for use;

Step S3: coating of anti-reflection film: take the cleaned glass substrate, apply anti-reflection film liquid on the surface of one side of the glass substrate by roller coating method, and cure at low temperature to form an anti-reflection film; the temperature during low-temperature curing is 300 ℃ ℃, the curing time is 2min;

Step S4: taking the treated glass substrate, coating a layer of photoresist on the side that is not coated with the anti-reflection film, and baking to cure the masking film to form a masking film; wherein the baking temperature is 100°C, and the baking time is 100°C. is 15min;

Step S5: Application of Self-Cleaning Coating:

Step S51: Preparation of polyvinyl alcohol, take the prepared methanol, put the methanol into a four-necked flask equipped with a stirrer, a condenser, a thermometer and a dropping funnel, add sodium hydroxide solution, turn on the stirrer and stir, and the stirring time is: 5min; then put the prepared vinyl acetate into the dropping funnel, slowly add it dropwise to the four-necked flask within 35min, and stir and react for 2.5h to obtain the first material;

Step S52: Coating of the adhesive layer: take the first material after the reaction, pour it into a beaker, then put the glass substrate treated in step 3) into the beaker, heat it up to 50°C, and react for 15 minutes; the beaker is heated The temperature was raised to 90°C, stirred at a constant temperature for 8 minutes, then put the prepared aluminum sulfate, starch, defoamer, and preservative into the beaker in turn, stirred for 5 minutes, and cooled to room temperature after stirring. At this time, a bonding layer was formed on the surface of the glass substrate, and then Take out the glass substrate and set aside;

Step S6: Coating of the modified silica gel layer: Take the prepared tetraethyl silicate and ethanol, put them into a beaker, perform magnetic stirring at room temperature, and then take the prepared ammonia water, and slowly add it dropwise to the beaker during the stirring process , after the dropwise addition of ammonia water, continue to stir for 260 min; stand for aging for 12 h to obtain silica gel; take the prepared heptadecafluorodecyltrimethoxysilane and γ-(2,3-glycidoxyloxy) ) propyltrimethoxysilane, diluted with ethanol, then put into a beaker in turn, and ultrasonically stirred for 2 h to obtain modified silica gel;

Take the glass substrate processed in step S5, place it on a glue-spinning platform, with the uncoated side facing down, drop the modified silica gel evenly, spin the glue for 2 min, and set the rotating speed to 1600 rpm; The plate was heated for 4 minutes, and the temperature of the hot plate was 90 °C; the glue was repeatedly thrown for 5 times, and then placed in an oven for thermosetting to form a modified silica gel layer; the thermosetting temperature was 100 °C, and the thermosetting time was 30min;

Step S7: removing the masking film: taking the processed glass substrate, removing the masking film on one side of the glass substrate, and then washing with deionized water for 4 times; the operation is ended.

In this embodiment, the thickness of the anti-reflection film is 100 nm, the thickness of the self-cleaning coating is 200 nm; the thickness of the adhesive layer is 100 nm, and the thickness of the modified silica gel layer is 100 nm .

The raw material components of the modified silica gel layer include: by weight, 25 parts of tetraethyl silicate, 20 parts of ethanol, 40 parts of ammonia water, 15 parts of heptadecafluorodecyl trimethoxysilane, 8 parts of the joint agent; the raw material components of the adhesive layer include: by weight, 16 parts of methanol, 30 parts of vinyl acetate, 10 parts of sodium hydroxide, 12 parts of aluminum sulfate, 5 parts of defoamer, 6 parts of preservatives parts and 6 parts of starch; the crosslinking agent is γ-(2,3-glycidoxy)propyltrimethoxysilane.

Experiment 1:

Take the coated glass samples prepared in Examples 1-3, and then take the self-cleaning coated glass purchased on the market to detect the water contact angle of the coated glass: the contact angle uses a static drop contact angle tester to test the contact angle of water droplets on the surface of the self-cleaning glass. Wetting angle, by measuring the contact angles of 5 different positions on the film surface, and taking the average value as the surface contact angle of the film, the results of the present invention are as follows:

After the samples in Examples 1-3 were tested, the water contact angles of the glass surfaces were 155°, 157°, and 151°, respectively; while the surface water contact angles of commercially available coated glass were 132°.

Conclusion: This technical solution discloses a coated glass with surface self-cleaning and a preparation method thereof. By modifying the silica gel, a superhydrophobic plane is formed on the surface of the coated glass, which effectively improves the superhydrophobicity and performance of the coated glass. Self-cleaning properties.

Experiment 2: The film adhesion of Examples 1-3 and the self-cleaning glass purchased in the market were tested respectively, and the results were as follows:

After the samples in Examples 1-3 were tested, the adhesion was 25N, 28N, and 23N, respectively, while the adhesion of commercially available coated glass was 11N.

Conclusion: This technical solution ensures that the adhesive layer can be smoothly and closely combined with the anti-reflection film by forming a rough surface on the anti-reflection film and at the same time generating the adhesive layer, and effectively improves the adhesion between the anti-reflection film and the modified silica gel layer. tightly bound.

It will be apparent to those skilled in the art that the present invention is not limited to the details of the above-described exemplary embodiments, but that the present invention may be embodied in other specific forms without departing from the spirit or essential characteristics of the invention. Therefore, the embodiments are to be regarded in all respects as illustrative and not restrictive, and the scope of the invention is to be defined by the appended claims rather than the foregoing description, which are therefore intended to fall within the scope of the claims. All changes within the meaning and scope of the equivalents of , are included in the present invention.

Claims (1)

1. A coated glass with a self-cleaning surface is characterized in that: the coated glass comprises a glass substrate, an antireflection film and a self-cleaning coating, wherein the antireflection film is coated on the surface of one side of the glass substrate, and the self-cleaning coating is coated on the antireflection film; the self-cleaning coating comprises an adhesive layer and a modified silicon dioxide gel layer, wherein the adhesive layer is coated on the antireflection film, and the modified silicon dioxide gel layer is coated on the adhesive layer;

the preparation method of the coated glass comprises the following steps:

step S1: preparing raw materials; weighing tetraethyl silicate, ethanol, ammonia water, heptadecafluorodecyltrimethoxysilane and gamma- (2, 3-epoxypropoxy) propyltrimethoxysilane according to a proportion for later use; weighing methanol, vinyl acetate, sodium hydroxide, aluminum sulfate, a defoaming agent, a preservative and starch according to a proportion for later use;

step S2: cleaning a glass substrate, wherein when the glass substrate is cleaned, the cut glass substrate is taken and put into a sodium hydroxide solution for soaking for 20min, then is washed by deionized water, and is dried by nitrogen for standby;

step S3: coating of an antireflection film: coating an antireflection film liquid on the surface of one side of the glass substrate by using a roll coating method, and curing at a low temperature to form an antireflection film; the low-temperature curing temperature is 280 ℃, and the curing time is 5 min;

step S4: coating a layer of photoresist on one side of the treated glass substrate which is not coated with the antireflection film, and baking to solidify the shielding film to form a shielding film; wherein the baking temperature is 95 ℃, and the baking time is 20 min;

step S5: coating of the self-cleaning coating:

step S51: preparing polyvinyl alcohol, namely putting prepared methanol into a four-neck flask provided with a stirrer, a condenser pipe, a thermometer and a dropping funnel, adding a sodium hydroxide solution, starting the stirrer to stir for 2 min; then placing the prepared vinyl acetate into a dropping funnel, slowly dropping the prepared vinyl acetate into a four-neck flask within 25min, and stirring for reacting for 1.5h to obtain a first material;

step S52: coating of the bonding layer: pouring the first material after the reaction is finished into a beaker, putting the glass substrate treated in the step 3) into the beaker, heating to 40 ℃, and reacting for 25 min; heating the beaker to 80 ℃, stirring at a constant temperature for 12min, sequentially adding the prepared aluminum sulfate, starch, defoaming agent and preservative into the beaker, stirring for 3min, cooling to room temperature after stirring, forming a bonding layer on the surface of the glass substrate, and taking out the glass substrate for later use;

step S6: coating of the modified silica gel layer: putting the prepared tetraethyl silicate and ethanol into a beaker, performing magnetic stirring at room temperature, slowly dropwise adding the prepared ammonia water into the beaker in the stirring process, and continuously stirring for 250min after dropwise adding of the ammonia water is finished; standing and aging for 10h to obtain silicon dioxide gel; diluting the prepared heptadecafluorodecyltrimethoxysilane and gamma- (2, 3-epoxypropoxy) propyltrimethoxysilane with ethanol, sequentially putting into a beaker, and ultrasonically stirring for 1h to obtain modified silica gel;

placing the glass substrate treated in the step S5 on a whirl coating platform, enabling the side, which is not coated with the masking film, to face downwards, uniformly and dropwise adding modified silica gel, wherein whirl coating is carried out for 1min, and the rotating speed is 1400 rpm; then placing on a hot plate and heating for 2min, wherein the temperature of the hot plate is 110 ℃; repeatedly throwing the gel for 3 times, and then putting the gel into an oven for thermosetting to form a modified silicon dioxide gel layer; wherein the thermosetting temperature is 90 ℃ and the thermosetting time is 40 min;

step S7: removing the masking film: taking the treated glass substrate, removing the masking film on one side of the glass substrate, and then cleaning for 2 times by using deionized water; finishing the operation;

the thickness of the antireflection film is 50nm, and the thickness of the self-cleaning coating is 100 nm; the thickness of the bonding layer is 50nm, and the thickness of the modified silicon dioxide gel layer is 50 nm;

the modified silica gel layer comprises the following raw material components: by weight, 15 parts of tetraethyl silicate, 10 parts of ethanol, 20 parts of ammonia water, 5 parts of heptadecafluorodecyltrimethoxysilane and 3 parts of a crosslinking agent; the bonding layer comprises the following raw material components: by weight, 8 parts of methanol, 15 parts of vinyl acetate, 5 parts of sodium hydroxide, 5 parts of aluminum sulfate, 3 parts of a defoaming agent, 3 parts of a preservative and 2 parts of starch; the cross-linking agent is gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane.