CN111848857A

CN111848857A - Resin pore-forming agent for antireflection coating liquid, preparation method thereof and antireflection coating liquid

Info

Publication number: CN111848857A
Application number: CN202010771520.8A
Authority: CN
Inventors: 郭玉楠; 游芳芳; 康正辉
Original assignee: Wujiang CSG Glass Co Ltd
Current assignee: Wujiang CSG Glass Co Ltd
Priority date: 2020-08-04
Filing date: 2020-08-04
Publication date: 2020-10-30
Anticipated expiration: 2040-08-04
Also published as: CN115093792A; CN115057960B; CN111848857B; CN115057960A; CN115093792B

Abstract

The invention discloses a resin pore-forming agent for an antireflection coating liquid, a preparation method thereof and the antireflection coating liquid, wherein the resin pore-forming agent comprises the following raw material components in percentage by mass: 34-45% of monomer composition, 54.5-65% of dispersing solvent and 0.5-1% of initiator. The invention synthesizes the resin pore-forming agent by taking the compatibility of the resin pore-forming agent and the silica sol and the interaction condition of the resin pore-forming agent and the silica sol in the film-forming, curing and toughening stages of the coating solution into comprehensive consideration through molecular design. The resin pore-forming agent not only can have better compatibility with the silica sol, but also can interact with the silica sol in the curing and toughening stage to realize surface closed pore of the anti-reflection film layer. The synthesis of the resin pore-forming agent can realize the closed pore on the surface of the film layer without adding hole sealing substances, reduce the types of raw materials in the formula of the antireflection coating liquid, and save the cost without complex preparation process, simple process and the like. Realizes the technical purpose of closed pores by using the least raw materials, and obtains the formula of the antireflection coating liquid with simple preparation.

Description

Resin pore-forming agent for antireflection coating liquid, preparation method thereof and antireflection coating liquid

Technical Field

The invention relates to the technical field of high polymer materials and coating solutions, in particular to a resin pore-forming agent for an antireflection coating solution, a preparation method thereof and the antireflection coating solution comprising the resin pore-forming agent.

Background

The antireflection coating toughened glass is toughened glass coated with antireflection coating liquid and is an important component of a solar cell module. With the continuous development and optimization of the solar photovoltaic market, the installation demand of the components is continuously increased, the installation environment range is continuously enlarged, the power gain requirement of the components is higher and higher, and accordingly, the industry has more stringent requirements on the anti-reflection, stain resistance and weather resistance of the anti-reflection coated toughened glass.

The advantages and disadvantages of the antireflection, stain resistance and weather resistance of the antireflection coated toughened glass are mainly determined by the porosity of the antireflection coating and the closure condition of the surface microstructure of the coating. The porosity of the antireflection film is mainly determined by the sintering condition of a pore-forming agent in the antireflection coating liquid in the film-forming, curing and toughening processes; if the surface of the antireflection film layer can form a closed pore structure, water vapor or pollutants in the environment can be prevented from invading the film layer to a great extent to corrode the film layer, and the stain resistance and weather resistance of the film layer are improved, so that the prepared closed pore antireflection film is a good technical route.

The sol-gel method is a common method for manufacturing the antireflective coating liquid for photovoltaic at present, and the antireflective coating liquid prepared by the method mainly comprises silica sol used as a film forming substance, an organic high molecular polymer used as a pore forming agent, a solvent, an auxiliary agent and the like. The silica sol is nano inorganic netted silica sol formed through hydrolysis and polycondensation of silane or siloxane in acid or alkali catalysis condition, and the sol has relatively great amount of active silica hydroxyl groups to provide active points for the cross-linking reaction with other components in the coating liquid. The selection of pore-forming agent as one of the core materials of the film-coating liquid largely determines the performance of the film-coating liquid, and emulsion mainly composed of styrene or polyurethane is reported as the pore-forming agent for a long time, and the report on the resin as the pore-forming agent is less. The selection of the resin for the antireflection coating liquid is mostly that whether the resin is compatible with a system is tested by searching the outsourced resin of a resin manufacturer, and whether the resin can meet the performance requirement of the coating liquid is tested even if the resin matched with the system is found, so that the test quantity is greatly increased; and the research and development of the purchased products are restricted by people, and most test phenomena cannot be reasonably analyzed and explained due to unknown structure and performance of the products, so that the research and development progress is greatly slowed down, and the independent research and development are difficult to realize, so that the synthesis of the resin pore-forming agent which has good system compatibility and meets the performance requirements according to the requirements of independently researching and developing the coating solution is particularly urgent.

The existing reports about the resin for the antireflection coating liquid mainly consider the compatibility problem of the resin and the silica sol. For example, the invention patent of Chinese patent application No. 201610666719.8 entitled "a high-permeability anti-fouling coating liquid and a preparation method thereof" provides a thought of a high-permeability anti-fouling antireflection coating liquid capable of realizing surface closed pores, and the coating liquid is prepared by dispersing a film forming substance solution, a pore forming substance solution and a closed pore substance solution in a solvent. The silicon sol is used as a film forming substance, a methacrylic resin solution is used as a pore forming agent to realize void ratio and increase permeability, and the final surface closed pores of the antireflection film layer are realized through a hole sealing substance solution, so that the high-permeability and anti-fouling coating liquid is obtained. However, the membrane layer closed pores in the patent need to be realized by the interaction of the sealing substances with the resin and the silica sol, and the sealing cannot be realized only by the interaction of the resin and the film forming substances.

For example, in chinese patent application No. 201710594700.1, the resin template agent in the invention named "a template agent for antireflective coating liquid and a preparation method and application thereof" comprises the following steps: (1) adding an alcohol or ether solvent into a reaction vessel; (2) sequentially adding an initiator and three or more monomers at the temperature of 60-110 ℃, wherein the monomer adding time is 2-6 h; (3) after the monomer is dripped, the temperature is kept for 5 to 14 hours; and (4) cooling, adding ammonia water or amine pH regulator to adjust the pH value of the resin to 7-10 when the temperature is reduced to 40-50 ℃, filtering and discharging to obtain the resin template agent. The template agent obtained by molecular design realizes good compatibility with silica sol, and finally the silane coupling agent is added to prepare coating liquid, thereby achieving the purpose of improving the anti-reflection and dirt resistance of the antireflection film. The technical idea is that better compatibility of resin and a system is realized mainly through molecular design, and no technical design scheme for realizing closed pores on the surface of the anti-reflection film layer through interaction of the resin and silica sol is involved; in addition, in the process of preparing the coating liquid, the silica sol and the template agent are mixed, the silane coupling agent is added, and then the heating reaction treatment is carried out, so that the step of preparing the coating liquid is redundant, and the energy consumption is high.

Disclosure of Invention

In view of the above, in order to overcome the defects of the prior art, the present invention aims to provide a resin pore-forming agent for an anti-reflective coating solution, and a preparation method of the resin pore-forming agent.

In order to achieve the purpose, the invention adopts the following technical scheme:

the resin pore-forming agent is obtained by copolymerization reaction initiated by a free radical initiator under the condition that a monomer composition exists in a dispersing solvent. The resin pore-forming agent comprises the following raw material components in percentage by mass:

34 to 45 percent of monomer composition

54.5 to 65 percent of dispersing solvent

0.5 to 1 percent of initiator

The monomer in the monomer composition is acrylic acid and/or derivatives thereof and/or styrene.

The monomer in the monomer composition is selected from 4 or more than 4 of methyl methacrylate, acrylic acid, methacrylic acid, butyl acrylate, isooctyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, styrene, tetrahydrofuran methacrylate, isobornyl methacrylate, acrylamide and N-hydroxymethyl acrylamide.

Preferably, the monomers in the monomer composition comprise methyl methacrylate and methacrylic acid.

More preferably, the monomers in the monomer composition further include butyl acrylate.

Also preferably, the monomers in the monomer composition further comprise acrylamide.

Still preferably, the monomer in the monomer composition further comprises hydroxyethyl acrylate.

Still preferably, the monomers in the monomer composition further include isooctyl acrylate, styrene, tetrahydrofuryl methacrylate, N-methylol acrylamide.

According to some preferred aspects of the invention, the monomers in the monomer composition comprise at least methyl methacrylate, butyl acrylate, methacrylic acid and acrylamide.

Preferably, the monomer composition comprises the following components in parts by weight:

according to some preferred aspects of the present invention, the dispersion solvent is an alcohol solvent and/or a high boiling point solvent, and the high boiling point solvent is one or more of propylene glycol methyl ether acetate, propylene glycol methyl ether, propylene glycol diacetate, and butyl acetate. In some embodiments, the dispersing solvent is selected from two or more of ethanol, isopropanol, n-butanol, ethylene glycol, butyl acetate, propylene glycol methyl ether, propylene glycol ethyl ether, ethylene glycol monobutyl ether. The alcohol solvent and/or the high-boiling point solvent are/is used, the benzene solvent or acetone with high toxicity is avoided, the boiling point of the mixed solvent in the reaction is ensured to be higher than the reaction temperature, and meanwhile, the reactant and the product can be dissolved in the solvent.

Preferably, the dispersing solvent is a mixed solution composed of ethanol and propylene glycol methyl ether acetate; the mixed solution comprises 80-150 parts by weight of ethanol and 100-160 parts by weight of propylene glycol methyl ether acetate.

Wherein, for the resin pore-forming agent for the antireflection coating liquid, the initiator is selected from one of benzoyl peroxide, azodiisobutyronitrile and azodiisoheptadecylamine.

The invention also provides a preparation method of the resin pore-forming agent for the anti-reflection coating liquid, which comprises the following steps:

a. adding a dispersing solvent into a reaction container, heating to 75-90 ℃, then preserving heat for 0.5h, beginning to dropwise add a mixed solution of a monomer composition and a part of an initiator, and finishing dropwise adding within 1-3 h;

b. after the dripping is finished, preserving the heat for 0.5h, dissolving the rest initiator in a dispersing solvent, dripping the initiator into the system in the step a, and finishing the addition within 10-25 min;

c. and (3) keeping the temperature for 1.5-3h after the initiator is added, cooling, filtering and discharging to obtain the resin pore-forming agent.

According to some preferred aspects of the invention, the mass ratio of the monomer to the initiator in the mixture of the monomer and the partial initiator is 50-80: 1.

According to some preferred aspects of the invention, the portion of initiator constitutes 60-80%, preferably 75%, of the total mass of initiator.

According to some preferred aspects of the invention, the remaining initiator in step b is dissolved in a dispersion solvent in a mass ratio of the dispersion solvent to the initiator of 25-35: 1.

The invention also provides an antireflection coating liquid which comprises the resin pore-forming agent. The anti-reflection coating liquid comprises the following components in percentage by mass:

the resin diluent comprises a resin pore-forming agent and a diluent, and the resin pore-forming agent comprises the following raw material components in percentage by mass:

34 to 45 percent of monomer composition

54.5 to 65 percent of dispersing solvent

0.5 to 1 percent of initiator.

According to some preferred aspects of the present invention, the mass ratio of the resin pore former to the diluent is: the diluent is 1: 3-8. In some embodiments, the mass ratio of the resin pore former to the diluent is 1: 4.

According to some preferred aspects of the present invention, the diluent comprises isopropyl alcohol and propylene glycol methyl ether acetate, and the mass ratio of the isopropyl alcohol to the propylene glycol methyl ether acetate is 1: 0.5-1.5. In some embodiments, the resin diluent is a resin pore former in a mass ratio of: isopropyl alcohol: PMA was diluted 1:2: 2.

The pH regulator is selected from one of triethylamine, triethanolamine and diethanolamine.

The invention also provides a preparation method of the antireflection coating liquid with the surface hole sealing function, which is characterized by comprising the following steps of:

A. dispersing a film-forming substance, namely silica sol, in a carrier solvent at normal temperature under the condition of starting stirring;

B. c, under continuous stirring, preparing a resin pore-forming agent into a resin diluent, and adding the resin diluent into the solution prepared in the step A;

C. and D, adding a pH regulator into the solution prepared in the step B, and continuously and uniformly stirring for 40min to obtain the antireflection coating liquid.

According to some preferred aspects of the present invention, the preparation of the silica sol comprises the steps of:

1) adding isopropanol into a reaction container, sequentially adding ethyl orthosilicate and a silane coupling agent, adding pure water and a catalyst, and uniformly stirring;

2) reacting for 3-6h at the temperature of 40-70 ℃, and cooling to room temperature to obtain the silica sol.

Wherein the isopropanol, the tetraethoxysilane, the silane coupling agent, the pure water and the catalyst are 52 to 58 percent, 3.3 to 4 percent, 30 to 33 percent, 9.5 to 11.5 percent and 0.005 to 0.015 percent by mass percent; the silane coupling agent is selected from two or more of methyltrimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, vinyltriethoxysilane, gamma- (2, 3-glycidoxy) propyltrimethoxysilane (KH-560), gamma-methacryloxypropyltrimethoxysilane (KH-570), phenyltrimethoxysilane and phenyltriethoxysilane; the catalyst is hydrochloric acid or acetic acid.

Due to the adoption of the technical scheme, compared with the prior art, the invention has the following benefits: the resin pore-forming agent suitable for the antireflection coating liquid can have good compatibility with silica sol, and can interact with the silica sol in the curing and toughening stage to realize surface closed pores of an antireflection coating layer. The method can realize the closed pores on the surface of the film layer without adding hole sealing substances, reduces the types of raw materials in the formula of the antireflection coating liquid, does not need a complex preparation process, has simple and convenient process and saves the cost. Realizes the technical purpose of closed pores by using the least raw materials, and obtains the formula of the antireflection coating liquid with simple preparation.

Drawings

In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.

FIG. 1 is an SEM photograph of the surface of an antireflection coating film in preferred embodiment 3 of the present invention;

fig. 2 is an SEM image of a cross section of the antireflection coating film in preferred embodiment 3 of the present invention.

Detailed Description

In order to make those skilled in the art better understand the technical solution of the present invention, the technical solution in the embodiment of the present invention will be clearly and completely described below with reference to the drawings in the embodiment of the present invention, and it is obvious that the described embodiment is only a part of the embodiment of the present invention, and not a whole embodiment. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

EXAMPLE 1 resin pore-forming agent and method for preparing the same

In this embodiment, the resin pore-forming agent for the anti-reflective coating solution is obtained by initiating a copolymerization reaction of a monomer composition in the presence of a dispersion solvent by a radical initiator.

The resin pore-forming agent comprises the following raw material components:

monomer composition 137.91g

Dispersion solvent 206.88g

Initiator 2.76g

In this example, the initiator is Azobisisobutyronitrile (AIBN), and the dispersion solvent is propylene glycol methyl ether acetate and ethanol. In other embodiments, the initiator is selected from one of benzoyl peroxide, azobisisobutyronitrile, azobisisoheptonitrile; the dispersion solvent is alcohol solvent and/or high boiling point solvent, the high boiling point solvent is one or more of propylene glycol methyl ether acetate, propylene glycol methyl ether, propylene glycol diacetate and butyl acetate, namely the dispersion solvent is two or more selected from ethanol, isopropanol, n-butanol, ethylene glycol, butyl acetate, propylene glycol methyl ether, propylene glycol ethyl ether and ethylene glycol monobutyl ether, and preferably the dispersion solvent is a mixed solution consisting of ethanol and propylene glycol methyl ether acetate.

The monomer composition in this example comprises the following components:

in some other embodiments, the monomers in the monomer composition are selected from 4 or more of methyl methacrylate, acrylic acid, methacrylic acid, butyl acrylate, isooctyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, styrene, tetrahydrofuryl methacrylate, isobornyl methacrylate, acrylamide, N-methylolacrylamide. Preferably, the monomers in the monomer composition include at least methyl methacrylate, butyl acrylate, methacrylic acid, and acrylamide.

The preparation method of the resin pore-forming agent in the embodiment comprises the following steps:

a. adding a weighed 103.44g of propylene glycol monomethyl ether acetate (PMA) and 83.44g of ethanol mixed solvent into a 500ml four-neck flask provided with a stirrer, a condenser and a dropping funnel, starting stirring, and starting heating after uniformly stirring;

b. after the temperature rises to 80 ℃, keeping the temperature for 0.5h, starting to dropwise add 70g of methyl methacrylate, 43.58g of butyl acrylate, 17.22g of methacrylic acid, 7.11g of acrylamide and 2.07g of Azodiisobutyronitrile (AIBN) which are weighed and uniformly mixed in a dropping funnel, and finishing dropping within 2 h;

c. after dripping, preserving heat for 30min, and dripping 0.69g of AIBN and 20g of PMA which are uniformly stirred; dripping off in 15 min;

d. and continuing to keep the temperature for 2h after dripping, cooling, filtering and discharging to obtain the resin pore-forming agent.

Example 2 silica Sol and method for producing the same

The silica sol in the embodiment comprises the following raw material components:

in this example, the silane coupling agent was methyltriethoxysilane and vinyltrimethoxysilane, and the catalyst was concentrated hydrochloric acid. In other embodiments, the isopropanol, the ethyl orthosilicate, the silane coupling agent, the pure water and the catalyst are 52-58%, 3.3-4%, 30-33%, 9.5-11.5% and 0.005-0.015% by mass; the silane coupling agent is selected from two or more of methyltrimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, vinyltriethoxysilane, gamma- (2, 3-glycidoxy) propyltrimethoxysilane (KH-560), gamma-methacryloxypropyltrimethoxysilane (KH-570), phenyltrimethoxysilane and phenyltriethoxysilane; the catalyst is hydrochloric acid or acetic acid.

The preparation method of the silica sol in the embodiment comprises the following steps:

1) 718.6g of isopropanol is firstly added into a three-neck flask, then 54.4g of ethyl orthosilicate, 364.1g of methyltriethoxysilane and 66.9g of vinyl trimethoxy silane are sequentially added, 148g of pure water and 0.18g of concentrated hydrochloric acid are added, and the mixture is uniformly stirred;

2) the temperature is raised to 55 ℃, the reaction is carried out for 5h, and the silica sol is obtained after cooling to the room temperature.

Example 3 antireflection coating solution and method for producing the same

The antireflection coating liquid in the embodiment comprises the following components:

in this embodiment, the carrier solvent is isopropanol, the film-forming substance is silica sol prepared in embodiment 2, the pH adjuster is triethanolamine, and in other embodiments, the carrier solvent may be selected with reference to the dispersion solvent in embodiment 1; the pH regulator is selected from one of triethylamine, triethanolamine and diethanolamine.

The resin diluent comprises the resin pore-forming agent and the diluent prepared in the example 1, wherein the mass ratio of the resin pore-forming agent to the diluent is that of the resin pore-forming agent: the diluent is 1: 3-8. The mass ratio of the resin pore-forming agent to the diluent in this example is 1:4, and the resin diluent in this example is the resin pore-forming agent in mass ratio: isopropyl alcohol: PMA was diluted 1:2: 2.

The preparation method of the antireflective coating liquid in the embodiment comprises the following steps:

A. 1220g of the silica sol of the film-forming substance obtained in example 2 was dispersed in 2044.4g of isopropyl alcohol under stirring at ordinary temperature;

B. adding 622g of resin diluent diluted by the resin pore-forming agent of example 1 into the solution prepared in step A with continuous stirring;

C. and C, adding 0.28g of triethanolamine into the solution prepared in the step B, and continuously and uniformly stirring for 40min to obtain the antireflection coating liquid.

Example 4 resin pore-forming agent and method for preparing the same

The resin pore-forming agent comprises the following raw material components:

monomer composition 156.82g

Dispersion solvent 291.24g

Initiator 3.15g

In this example, the initiator Azobisisobutyronitrile (AIBN) was used, and the dispersion solvent was propylene glycol monomethyl ether acetate and ethanol.

The monomer composition in this example comprises the following components:

a. adding a weighed 149.74g of propylene glycol monomethyl ether acetate (PMA) and 116.5g of ethanol mixed solvent into a 500ml four-neck flask provided with a stirrer, a condenser and a dropping funnel, starting stirring, and starting heating after uniformly stirring;

b. after the temperature rises to 85 ℃, and the temperature is kept for 0.5h, 80.6g of methyl methacrylate, 41.27g of butyl acrylate, 19.80g of methacrylic acid, 9.81g of acrylamide, 5.34g of hydroxyethyl acrylate and 2.35g of Azobisisobutyronitrile (AIBN) which are weighed and uniformly mixed in a dropping funnel are started to be dripped, and dripping is finished for 2 h;

c. after dripping, preserving heat for 30min, and dripping 0.80g of AIBN and 25g of PMA which are uniformly stirred; dripping off in 15 min;

EXAMPLE 5 preparation of silica Sol

in this example, the silane coupling agent was methyltriethoxysilane and vinyltrimethoxysilane, and the catalyst was concentrated hydrochloric acid.

1) 870.9g of isopropanol is firstly added into a three-neck flask, then 62.50g of ethyl orthosilicate, 392.3g of methyl triethoxysilane and 76.1g of vinyl trimethoxy silane are sequentially added, 162g of pure water and 0.21g of concentrated hydrochloric acid are added, and the mixture is uniformly stirred;

2) the temperature is increased to 65 ℃, the reaction is carried out for 4h, and the reaction product is cooled to room temperature to obtain the silica sol.

Example 6 antireflection coating solution and method for producing the same

in this embodiment, the carrier solvent is isopropanol, the film-forming substance is silica sol prepared in embodiment 5, the pH adjuster is triethanolamine, and in other embodiments, the carrier solvent may be selected with reference to the dispersion solvent in embodiment 4; the pH regulator is selected from one of triethylamine, triethanolamine and diethanolamine.

The resin diluent comprises the resin pore-forming agent and the diluent prepared in the embodiment 4, and the mass ratio of the resin pore-forming agent to the diluent is that the resin pore-forming agent: the diluent is 1: 3-8. The mass ratio of the resin pore-forming agent to the diluent in this example is 1:4, and the resin diluent in this example is the resin pore-forming agent in mass ratio: isopropyl alcohol: PMA was diluted 1:2: 2.

A. 1295.68g of the silica sol of the film-forming substance obtained in example 5 was dispersed in 2104g of isopropyl alcohol under stirring at room temperature;

B. adding 600g of resin diluent diluted by the resin pore-forming agent in example 4 into the solution prepared in step A under continuous stirring;

C. and C, adding 0.32g of triethanolamine into the solution prepared in the step B, and continuously and uniformly stirring for 40min to obtain the antireflection coating liquid.

Comparative example 1

The preparation method of the comparative example is basically the same as that of the examples 1 to 3, and the main difference is that the formula of each component in the comparative example is different during synthesis, specifically, the silane ratio and the resin monomer ratio in the silica sol are adjusted to a certain degree.

The antireflection coating liquid in the comparative example comprises the following components:

preparation of silica sol

The silica sol in this comparative example comprises the following raw material components:

1) 792.97g of isopropanol is firstly added into a three-neck flask, then 62.50g of ethyl orthosilicate, 480.6g of methyl triethoxysilane and 57.09g of vinyl trimethoxy silane are sequentially added, and then 173.3g of pure water and 0.21g of concentrated hydrochloric acid are added and stirred uniformly;

2) the temperature is raised to 60 ℃, the reaction is carried out for 4h, and the silica sol is obtained after cooling to room temperature.

(II) preparation of the pore-forming resin used in this comparative example

The monomers in the resin pore former in this comparative example included the following components:

the preparation method of the resin pore-forming agent in the comparative example comprises the following steps:

a. adding a weighed 115.44g of propylene glycol monomethyl ether acetate (PMA) and 105.4g of ethanol mixed solvent into a 500ml four-neck flask provided with a stirrer, a condenser and a dropping funnel, starting stirring, and starting heating after uniformly stirring;

b. after the temperature rises to 80 ℃, keeping the temperature for 0.5h, beginning to dropwise add 70g of methyl methacrylate, 48.72g of butyl acrylate, 13.76g of methacrylic acid, 2.84g of acrylamide, 6.96g of hydroxyethyl acrylate and 2.13g of Azobisisobutyronitrile (AIBN) which are weighed and uniformly mixed in a dropping funnel, and finishing dropping within 2 h;

c. after dripping, preserving heat for 30min, and dripping 0.71g AIBN and 15g PMA which are uniformly stirred; dripping off in 15 min;

The preparation method of the coating liquid in the comparative example is similar to that of the example 3.

Comparative example 2

The preparation methods of the antireflective coating liquid and the silica sol in the comparative example are similar to those in examples 1 to 3, and the main difference is that the resin used in the resin diluent is a common commercially available resin.

wherein the pH regulator is triethanolamine, the carrier solvent is isopropanol, the film-forming substance is the same as the silica sol used in example 3, and the resin used in the resin diluent is AC-749RG type resin of Zhuhaijili chemical industry Co., Ltd.

The preparation method of the coating solution in the comparative example is similar to that of example 3.

Example 7 measurement of performance of antireflection coating liquid

1. Scanning the microstructure of the antireflection coating toughened glass plated by the antireflection coating liquid prepared in the example 3 by using an SEM, wherein images of the surface and the section of the antireflection coating toughened glass are shown in the attached drawings 1 and 2.

Figures 1 and 2 show: fig. 1 shows that the surface of the antireflection coating toughened glass obtained by the antireflection coating liquid prepared in example 3 is sealed; the cross section chart shows that the resin pore-forming agent and the silica sol in the antireflection coating liquid are subjected to a cross-linking reaction in a curing, toughening and sintering film-forming stage, so that a structural basis is provided for the performances of the film layer such as hardness, adhesive force, wear resistance and the like, and the sintered film layer has a certain porosity, so that the basis for realizing high antireflection of the antireflection film is realized.

2. The antireflection coating liquids prepared in example 3 and comparative examples 1 and 2 were coated on a photovoltaic glass substrate, and the antireflection coated tempered glass formed after curing and tempering was subjected to the following tests, and the antireflection and various performances were listed in the following table.

TABLE 1 result of antireflection coating test

It can be seen from table 1 that the antireflection coated glass obtained in example 3 has a higher antireflection than those obtained in comparative examples 1 and 2, and the other properties are superior to those of the glass obtained in the comparative examples. This is because the ratio of silane in the silica sol and the ratio of monomer in the resin change, which results in that the synthesized coating solution cannot form a film structure with sealed surfaces during the film-forming and sintering stage, and as a result, the effective porosity and anti-fouling performance of the film are deteriorated.

The test method of the above test is as follows:

1) and (3) testing pencil hardness: according to the national standard GB/T3098.1-2015, the hardness is required to be higher than 3H.

2) Testing of tape prints: A3M Scotch610-1PK type adhesive tape is used for rapid testing, the testing method comprises the steps of flatly laying the 3M adhesive tape and adhering the 3M adhesive tape to the surface of a film layer, forcibly extruding and grinding the adhesive tape by using dust-free cloth, then vertically tearing the adhesive tape at 90 degrees, and judging the adhesive tape to be 1-5 grade, 1 grade without mark, 2 grade to be very slight, 3 grade to be obvious, 4 grade residual white and bright marks and 5 grade degumming, wherein the larger the grade is, the worse the dirt resistance is.

3) Testing of polyethylene-vinyl acetate polymer (EVA) adhesive films: cleaning and drying the coated glass, and placing three pieces of coated glass with the area of about 2.5cm on the surface of the glass²The 3M polyethylene-vinyl acetate copolymer (EVA) adhesive film is prepared by placing a coated glass sample sheet with EVA in an oven (with the temperature set at 150 ℃), baking for 30min, taking out and cooling to room temperature, tearing off the EVA adhesive film on the surface of the glass by using tweezers, wiping with alcohol, observing whether the film surface has marks, judging the film surface to be 1-3 grade according to the depth of the marks on the residual surface, judging the film surface to be 1 grade without marks to have no change, judging the film surface to be 2 grade with slight marks to have light color, and judging the film surface to be 3 grade with obvious white marks, wherein the film surface color cannot be seen. The larger the number of stages, the worse the fouling resistance of the membrane surface.

4) Testing handprints: cleaning and drying the coated glass, pressing a fingerprint at the center of the surface of the glass, putting a coated glass sample wafer with the fingerprint into an oven (with the temperature set at 150 ℃), baking for 30min, taking out and cooling to room temperature, wiping with alcohol, observing whether the mark is left on the film surface, judging the mark to be 1-5 grade, 1 grade without mark, 2 grade with very slight mark, 3 grade with slight mark, 4 grade with relatively clear mark and 5 grade with very clear mark according to the depth of the residual surface mark. The larger the number of stages, the worse the fouling resistance of the membrane surface.

The invention synthesizes the resin pore-forming agent by taking the compatibility of the resin pore-forming agent and the silica sol and the interaction condition of the resin pore-forming agent and the silica sol in the film-forming, curing and toughening stages of the coating solution into comprehensive consideration through molecular design. The resin pore-forming agent not only can have better compatibility with the silica sol, but also can interact with the silica sol in the curing and toughening stage to realize surface closed pore of the anti-reflection film layer. The synthesis of the resin pore-forming agent can realize the closed pore on the surface of the film layer without adding hole sealing substances, reduce the types of raw materials in the formula of the antireflection coating liquid, and save the cost without complex preparation process, simple process and the like. Realizes the technical purpose of closed pores by using the least raw materials, and obtains the formula of the antireflection coating liquid with simple preparation.

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

(1) after comprehensively considering the characteristics of silica sol in the antireflection coating solution and the film-forming mechanism of solidifying and toughening an antireflection film, the invention synthesizes the acrylic resin pore-forming agent in a targeted manner through molecular design; the resin pore-forming agent has good compatibility with the silica sol, not only can play the function of the pore-forming agent in a system, but also can realize the surface closed pore of the film layer through the interaction of the curing and toughening process and the silica sol under the condition of not adding a hole sealing auxiliary agent, thereby preventing external water vapor or pollutants from invading into the film layer to cause corrosion to the film layer to a great extent; the microstructure provides guarantee for the anti-reflection, stain-resistant and weather-resistant performances of the anti-reflection film layer;

(2) the resin pore-forming agent prepared by the technical scheme has good compatibility with self-developed silica sol and the whole system, and the resin pore-forming agent and the silica sol are diluted by isopropanol and are adjusted in pH by triethanolamine to obtain stable anti-reflection coating liquid; under the condition of no need of adding hole sealing substances, the resin pore-forming agent and the silica sol are subjected to a crosslinking reaction in a film forming stage and are subjected to curing, tempering and sintering to obtain an antireflection film layer with closed surfaces, so that external water or pollutants are prevented from entering the corrosion film layer, the pollution resistance of the antireflection film is structurally guaranteed, a technical route of hole sealing is realized by a simple formula, and the antireflection and pollution resistance performances equivalent to those of the prior art are achieved; meanwhile, the anti-reflection coating liquid has a simple formula, the raw materials are also common and commercially available, the cost is low, and the process is simple.

The above embodiments are merely illustrative of the technical concept and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the content of the present invention and implement the invention, and not to limit the scope of the invention, and all equivalent changes or modifications made according to the spirit of the present invention should be covered by the scope of the present invention.

Claims

1. The resin pore-forming agent for the antireflection coating liquid is characterized by comprising the following raw material components in percentage by mass:

34 to 45 percent of monomer composition

54.5 to 65 percent of dispersing solvent

0.5 to 1 percent of initiator

2. The resin pore former according to claim 1, wherein the monomers in the monomer composition are selected from 4 or more of methyl methacrylate, acrylic acid, methacrylic acid, butyl acrylate, isooctyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, styrene, tetrahydrofuryl methacrylate, isobornyl methacrylate, acrylamide, and N-methylolacrylamide.

3. The resin pore former of claim 2, wherein the monomers in the monomer composition comprise at least methyl methacrylate, butyl acrylate, methacrylic acid, and acrylamide.

4. The resin pore former as claimed in claim 3, wherein the monomer composition comprises the following components in parts by weight:

5. the resin pore former as claimed in claim 1, wherein the dispersing solvent is an alcohol solvent and/or a high boiling point solvent, and the high boiling point solvent is one or more of propylene glycol methyl ether acetate, propylene glycol methyl ether, propylene glycol diacetate, and butyl acetate.

6. The method for preparing the resin pore-forming agent for the anti-reflective coating liquid according to claim 1, comprising the steps of:

a. heating the dispersion solvent, preserving the temperature, and dropwise adding a mixed solution formed by the monomer composition and part of the initiator into the dispersion solvent;

b. after finishing dropping, preserving heat, dissolving the rest initiator in a dispersing solvent and dropping the initiator into the system in the step a;

c. and (3) keeping the temperature after adding the initiator, and then cooling, filtering and discharging to obtain the resin pore-forming agent.

7. The method of claim 6, wherein the mass ratio of the monomer to the initiator in the mixture of the monomer and the partial initiator is 50-80: 1.

8. The method of preparing a resin pore-forming agent as claimed in claim 6, wherein the portion of the initiator is 60-80% by mass of the total amount of the initiator.

9. The method of claim 6, wherein the residual initiator in step b is dissolved in a dispersion solvent, and the mass ratio of the dispersion solvent to the initiator in this step is 25-35: 1.

10. An antireflection coating liquid characterized by comprising the resin pore-forming agent according to any one of claims 1 to 5.