CN109852157B - High-hardness AR coating liquid and preparation method thereof - Google Patents
High-hardness AR coating liquid and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the technical field of anti-reflection coating liquid, in particular to high-hardness AR coating liquid and a preparation method thereof. On one hand, the particle size of the synthesized fine-particle-size self-crosslinking styrene-acrylic emulsion reaches 50-90 nm by optimizing and adjusting the formula and the process of the template agent, so that the hardness of the AR coating is greatly improved; on the other hand, the invention introduces boron, aluminum, zirconium metal oxide and other crosslinking aids, thereby enhancing the three-dimensional network structure of the film layer, further improving the hardness of the film layer, and simultaneously having the characteristics of high permeability increase and strong weather resistance.
Description
Technical Field
The invention relates to the technical field of anti-reflection and anti-reflection coating liquid, in particular to high-hardness AR coating liquid and a preparation method thereof.
Background
The sol-gel method is a common method for preparing an anti-reflection coating (AR coating for short) solution of ultra-white photovoltaic glass, wherein the AR coating solution prepared by the sol-gel method mainly comprises silica sol, a template agent, a solvent and the like, silicate is used as a raw material, hydrolysis, polycondensation and other reactions are carried out under the catalysis of acid or alkali to generate nano silica sol with a three-dimensional network structure or a linear network structure, then the nano silica sol and the template agent are subjected to a compounding test under a certain condition to prepare the AR coating solution, the AR coating solution is formed into a film on an ultra-white photovoltaic glass substrate, and the film is solidified and toughened to form the AR coating. The silica sol prepared by acid catalysis has small particle size, firm combination with a glass substrate and high hardness, has industrial application value, but has the defects of low porosity and high refractive index of a film layer, and the prepared AR coating film has low light transmittance and can not meet the requirement of high anti-reflection coated glass; the silica sol prepared by alkali catalysis has large particle size and high porosity of the film, and the prepared AR coating has high light transmittance, but has the defects of insecure combination of the film and a glass substrate, easy falling and low industrial application value.
As an improvement of the prior art, the invention patent with application number 201710594700.1, which has been applied by the inventor, discloses a template agent for an anti-reflection coating liquid, and a preparation method and application thereof, and the technical scheme is that silica sol with good compatibility with the template agent is synthesized through molecular design according to the characteristics of different silica sols, so that the stability of the AR coating liquid is enhanced, the film forming property of the AR coating liquid is improved, and the anti-reflection rate is improved. However, although the method improves the anti-reflection rate, the particle size of the synthesized template emulsion can only reach 90-120nm, and the hardness of the prepared AR coating film cannot meet the market demand of high-hardness AR coating films.
The hardness of the AR coating liquid in the current market mainstream is lower (less than or equal to 3H), and the coating layer of the glass is easily scratched in the assembly installation and use processes, so that the appearance and the service performance of the glass are influenced. With the development of the photovoltaic industry in recent years, the requirements of customers on AR coated glass are higher and higher, especially higher requirements on the hardness of AR coating are provided, and high-hardness and high-anti-reflection coated glass is the industry development trend in the future.
Disclosure of Invention
The invention aims to provide a high-hardness AR coating liquid and a preparation method thereof aiming at the defects in the prior art, the hardness of the prepared AR coating liquid is greatly improved, and the prepared AR coating liquid has the characteristics of high permeability increase and strong weather resistance.
The purpose of the invention is realized by the following technical scheme:
the high-hardness AR coating liquid mainly comprises the following raw materials in percentage by mass:
10-25% of fine-particle-size self-crosslinking styrene-acrylic emulsion
15-35% of boron-aluminum-zirconium hybrid silica sol
0.1 to 1.5 percent of coupling agent
0.1 to 1.5 percent of cross-linking agent
40-60% of wet film volatilization control agent;
wherein:
the fine-particle-size self-crosslinking styrene-acrylic emulsion is prepared from the following raw materials in percentage by mass:
53 to 84 percent of deionized water
5 to 15 percent of emulsifier
1 to 2 percent of initiator
10-30% of mixed monomer;
the boron-aluminum-zirconium hybrid silica sol is prepared from the following raw materials:
5-10 ml of solvent
0.4-1.6 ml of deionized water
0.01-0.1 g of boron salt
Aluminum salt 0.01-0.1 g
0.01-0.1 g of zirconium salt
0.01-0.1 ml of catalyst
1ml of alkoxysilane.
In the technical scheme, the high-hardness AR coating liquid further comprises an auxiliary agent, wherein the auxiliary agent is at least one of a leveling agent, a dispersing agent, a wetting agent, a defoaming agent, a wear-resistant anti-scraping agent and a hardening agent, and the total mass percentage of the auxiliary agent is 0.1-2%.
In the technical scheme, the particle size of the fine-particle-size self-crosslinking styrene-acrylic emulsion is 50-90 nm.
In the technical scheme, the emulsifier is at least one of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, potassium abietate, sodium succinate sulfonate, dodecyl ammonium chloride, hexadecyl trimethyl ammonium bromide, hexadecyl pyridine bromide, Span40, Span60, Span80, Tween40, Tween60 and Tween 80;
the initiator is at least one of ammonium persulfate, sodium persulfate, potassium persulfate, azobisisobutylamidine hydrochloride, azobisisobutylimidazoline hydrochloride, azobiscyanovaleric acid, azobisdiisopropylimidazoline, cumene hydroperoxide, tert-butyl hydroperoxide, benzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide and peroxydicarbonate;
the mixed monomer is at least one of styrene, acrylic acid, methacrylic acid, itaconic acid, maleic anhydride, methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, butyl acrylate, isooctyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, N-methylol acrylamide, dibutyl itaconate, isobornyl methacrylate, diethylene glycol dibutyl acrylate, glycidyl methacrylate and diallyl phthalate.
In the technical scheme, the solvent is at least one of methanol, ethanol, ethylene glycol, n-propanol, isopropanol, propylene glycol, glycerol, n-butanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, dipropylene glycol methyl ether, propylene glycol dimethyl ether, tripropylene glycol monomethyl ether and tripropylene glycol monoethyl ether;
the catalyst is one or more of hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, acetic acid, citric acid, oxalic acid, sodium hydroxide, potassium hydroxide, urea, ethylamine, ethylenediamine or triethylamine;
the boron salt is at least one of boric acid, sodium tetraborate, zinc borate, sodium borohydride, potassium borohydride, diboron trioxide, borax and aluminum diboride; the aluminum salt is at least one of aluminum nitrate, aluminum chloride, aluminum phosphate, aluminum formate, aluminum acetate, aluminum propionate, dialkyl aluminum chloride, monoalkyl aluminum dichloride, trialkyl aluminum trichloride, aluminum isopropoxide and aluminum acetylacetonate; the zirconium salt is at least one of zirconium dioxide, zirconium chloride, zirconium nitrate, zirconium hydrogen phosphate, zirconium acetate, zirconium carbonate, zirconium oxychloride, zirconium ethoxide, zirconium propoxide, zirconium isopropoxide and zirconium acetylacetonate;
the alkoxy silane is at least one of tetraethoxy silane, methyltrimethoxy silane and methyltriethoxy silane.
In the technical scheme, the coupling agent is at least one of KH550, KH560 and KH 570; the cross-linking agent is at least one of methyltrimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, dimethyldimethoxysilane and phenyltriethoxysilane; the wet film volatilization control agent is at least one of deionized water, methanol, ethanol, ethylene glycol, n-propanol, isopropanol, propylene glycol, glycerol, n-butanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, dipropylene glycol methyl ether, propylene glycol dimethyl ether, tripropylene glycol monomethyl ether and tripropylene glycol monoethyl ether.
The invention also provides a preparation method of the high-hardness AR coating liquid, which comprises the following steps:
step a, synthesizing fine-particle-size self-crosslinking styrene-acrylic emulsion:
a1) adding deionized water into a reaction vessel according to the mass percentage, heating to 65-75 ℃ under the stirring state, adding an emulsifier, stirring for a certain time, then heating to 75-85 ℃, adding 0.5-1.5% of an initiator, and continuing to stir for a period of time;
a2) after the temperature is stable, beginning to dropwise add the mixed monomer with the mass percentage of 3-6%, stopping dropwise adding after 15-20 min, continuing dropwise adding the rest mixed monomer after the solution has obvious blue light and the temperature is stable, and completing dropwise adding within 1-3 h;
a3) preserving heat for 2-5 h at 75-85 ℃, then heating to 85-95 ℃, adding the rest initiator, and preserving heat for 1-3 h to obtain a fine-particle-size self-crosslinking styrene-acrylic emulsion;
b, preparing boron, aluminum and zirconium hybrid silica sol:
b1) adding a solvent and deionized water into a reaction vessel, adding boron salt, aluminum salt, zirconium salt and alkoxy silane under the condition of stirring, and heating to 25-60 ℃;
b2) after the temperature is stable, slowly dropwise adding the uniformly mixed solution of deionized water and a catalyst into a reaction vessel for 15-30 min, keeping the temperature constant in the dropwise adding process, then carrying out heat preservation reaction for 2-5 h, cooling to room temperature, and aging for 5-10 d to obtain boron-aluminum-zirconium hybrid silica sol;
step c, preparing high-hardness AR coating liquid:
c1) adding boron-aluminum-zirconium hybrid silica sol into a reaction vessel according to the mass percentage, slowly adding the fine-particle-size self-crosslinking styrene-acrylic emulsion into the reaction vessel under the condition of stirring at room temperature, continuously stirring for a period of time, then respectively adding a coupling agent and a crosslinking agent, preserving heat for 2-10 hours at the temperature of 25-60 ℃, and cooling to room temperature to obtain a compound liquid;
c2) and under the condition of stirring at room temperature, continuously stirring the wet film volatilization control agent in the compound solution for 1.5-2.5 h to obtain the high-hardness AR coating solution.
In the technical scheme, in the step a1, the emulsifier is added and stirred for 10-15 min; the stirring time for adding the initiator is 2-5 min.
In the technical scheme, in the step b1, the volume ratio of the solvent to the deionized water to the alkoxy silane is (5-10): (0.2-0.8): 1;
in the step b2, the volume ratio of the deionized water to the catalyst to the alkoxysilane in the step b1 is (0.2-0.8): (0.01-0.1): 1.
in the technical scheme, in the step c1, after slowly adding the fine-particle-size self-crosslinking styrene-acrylic emulsion into a reaction vessel, continuously stirring for 10-30 min
The invention has the beneficial effects that:
the invention relates to a high-hardness AR coating liquid which is mainly prepared from auxiliary agents such as fine-particle-size self-crosslinking styrene-acrylic emulsion, boron-aluminum-zirconium hybrid silica sol, coupling agent, crosslinking agent, wet film volatilization control agent and the like. Compared with the prior art, the invention enables the particle size of the synthesized fine-particle-size self-crosslinking styrene-acrylic emulsion to be reduced to 50-90 nm by optimizing and adjusting the formula and the process of the template agent, and enhances the structural performance of the film layer and greatly improves the hardness of the AR coating film due to the reduction of the inner pore size of the film layer under the condition of consistent porosity of the final film layer by adjusting the size and the arrangement distribution condition of pores in the film layer; on the other hand, the formula of the invention introduces boron, aluminum, zirconium metal oxide and other cross-linking auxiliary agents, thereby enhancing the three-dimensional network structure of the film layer, further improving the hardness of the film layer, and having the characteristics of high anti-reflection and strong weather resistance; in addition, because the film layer volatilizes along with the volatilization of organic matters in the high-temperature firing process, a certain impact effect is generated on the film layer to generate microcracks on the surface of the film layer, boron elements with smaller molecular weight are introduced in the synthesis process of the boron-aluminum-zirconium hybrid sol, and the boron elements can have good repairing effect on the microcracks on the surface of the film layer generated in the subsequent high-temperature treatment process, so that the hardness of the film layer is further improved.
Detailed Description
The invention is further described with reference to the following examples.
Example 1:
the preparation method of the high-hardness AR coating solution of the embodiment includes the following steps (the following components are all calculated by mass percent):
step a, synthesizing fine-particle-size self-crosslinking styrene-acrylic emulsion:
a1) adding 53% of deionized water into a reaction vessel, heating to 72 ℃ under the stirring state, adding 15% of emulsifier, stirring for 13min, heating to 83 ℃, adding 1.5% of initiator, and continuing stirring for 3 min;
a2) after the temperature is stable, starting to dropwise add 6% of mixed monomers, stopping dropwise adding after 18min, continuing to dropwise add 24% of mixed monomers after the solution has obvious blue light and the temperature is stable, and completing dropwise adding within 2 h;
a3) keeping the temperature at 83 ℃ for 3h, then heating to 90 ℃, adding 0.5 percent of initiator, keeping the temperature for 1.5h, and obtaining the fine-particle-size self-crosslinking styrene-acrylic emulsion with the particle size of 70 nm.
B, preparing boron, aluminum and zirconium hybrid silica sol:
b1) adding a solvent and deionized water into a reaction vessel, adding boron salt, aluminum salt, zirconium salt and alkoxy silane under the condition of stirring, and heating to 40 ℃; in the step, the volume ratio of the solvent to the deionized water to the alkoxy silane is 6: 0.2: 1;
b2) after the temperature is stable, slowly dropwise adding the uniformly mixed solution of deionized water and the catalyst into a reaction vessel for 25min, keeping the temperature constant in the dropwise adding process, then carrying out heat preservation reaction for 3h, cooling to room temperature, and aging for 8d to obtain boron-aluminum-zirconium hybrid silica sol; in the step, the volume ratio of deionized water, catalyst and alkoxy silane is 0.6: 0.05: 1.
step c, preparing high-hardness AR coating liquid:
c1) adding 15% of boron-aluminum-zirconium hybrid silica sol into a reaction vessel, slowly adding 23% of fine-particle-size self-crosslinking styrene-acrylic emulsion into the reaction vessel under the condition of stirring at room temperature, continuously stirring for 25min, then respectively adding 1.5% of coupling agent and 1.0% of crosslinking agent, preserving heat for 6h at the temperature of 45 ℃, and cooling to room temperature to obtain a compound liquid;
c2) and under the condition of stirring at room temperature, adding 60% of wet film volatilization control agent, 0.6% of flatting agent and 0.8% of wetting agent into the compound liquid, and continuously stirring for 2 hours to obtain the high-hardness AR coating liquid.
In the embodiment, in the step a, the emulsifier is formed by mixing sodium dodecyl sulfate and sodium dodecyl benzene sulfonate according to a mass ratio of 1: 2; the initiator is ammonium persulfate; the mixed monomer is a mixture of styrene, methacrylic acid and ethyl acrylate according to the mass ratio of 3:1: 1.
In the step b, the solvent is a mixture of methanol and propylene glycol according to a mass ratio of 2: 3; the catalyst is a mixture of phosphoric acid, citric acid and oxalic acid according to a mass ratio of 2:2: 5; the boron salt is a mixture of sodium tetraborate and sodium borohydride in a mass ratio of 1: 2; the aluminum salt is a mixture of aluminum nitrate, aluminum chloride and aluminum phosphate according to a mass ratio of 1:3: 4; the zirconium salt is a mixture of zirconium dioxide and zirconium chloride according to a mass ratio of 5: 1; the alkoxysilane is tetraethoxysilane.
In the step c, the coupling agent is a mixture of KH550, KH560 and KH570 in a mass ratio of 3:5: 2; the cross-linking agent is a mixture of methyltrimethoxysilane and methyltriethoxysilane according to a mass ratio of 4: 1; the wet film volatilization control agent is a mixture of ethanol, ethylene glycol and n-propanol according to a mass ratio of 3:4: 2.
Example 2:
the preparation method of the high-hardness AR coating solution of the embodiment includes the following steps (the following components are all calculated by mass percent):
step a, synthesizing fine-particle-size self-crosslinking styrene-acrylic emulsion:
a1) adding 65% of deionized water into a reaction vessel, heating to 68 ℃ under the stirring state, adding 12% of emulsifier, stirring for 12min, heating to 79 ℃, adding 0.8% of initiator, and continuing stirring for 4 min;
a2) after the temperature is stable, beginning to dropwise add 4.9% of mixed monomers, stopping dropwise adding after 15min, continuing to dropwise add 17% of mixed monomers after the solution has obvious blue light and the temperature is stable, and completing dropwise adding within 2 h;
a3) keeping the temperature at 79 ℃ for 4h, then heating to 92 ℃, adding 0.3% of initiator, and keeping the temperature for 2h to obtain the fine-particle-size self-crosslinking styrene-acrylic emulsion with the particle size of 50 nm.
B, preparing boron, aluminum and zirconium hybrid silica sol:
b1) adding a solvent and deionized water into a reaction vessel, adding boron salt, aluminum salt, zirconium salt and alkoxy silane under the condition of stirring, and heating to 25 ℃; in the step, the volume ratio of the solvent to the deionized water to the alkoxy silane is 10: 0.8: 1;
b2) after the temperature is stable, slowly dropwise adding the uniformly mixed solution of deionized water and the catalyst into a reaction vessel for 30min, keeping the temperature constant in the dropwise adding process, then carrying out heat preservation reaction for 5h, cooling to room temperature, and aging for 10d to obtain boron-aluminum-zirconium hybrid silica sol; in the step, the volume ratio of deionized water, catalyst and alkoxy silane is 0.2: 0.01: 1.
step c, preparing high-hardness AR coating liquid:
c1) adding 16% of boron-aluminum-zirconium hybrid silica sol into a reaction vessel, slowly adding 27% of fine-particle-size self-crosslinking styrene-acrylic emulsion into the reaction vessel under the condition of stirring at room temperature, continuously stirring for 20min, then respectively adding 1.0% of coupling agent and 0.6% of crosslinking agent, preserving heat for 4h at 35 ℃, and cooling to room temperature to obtain a compound liquid;
c2) and under the condition of stirring at room temperature, adding 55% of a wet film volatilization control agent and 0.4% of a dispersing agent into the compound solution, and continuously stirring for 1.5h to obtain the high-hardness AR coating solution.
In the embodiment, in the step a, the emulsifier is a mixture of Span40 and Tween60 according to a mass ratio of 5: 1;
the initiator is a mixture of azodiisobutyl amidine hydrochloride and azodicyano valeric acid according to the mass ratio of 2: 1; the mixed monomer is a mixture of phenethyl methacrylate, hydroxypropyl methacrylate, N-hydroxymethyl acrylamide and isobornyl methacrylate according to the mass ratio of 1:2:3: 3.
In the step b, the solvent is a mixture of propylene glycol dimethyl ether, tripropylene glycol monomethyl ether and tripropylene glycol monoethyl ether according to a mass ratio of 3:2: 2; the catalyst is a mixture of sodium hydroxide and potassium hydroxide according to a mass ratio of 4: 3.
The boron salt is a mixture of boric acid, diboron tetratrioxide and aluminum diboride in a mass ratio of 1:5: 1; the aluminum salt is a mixture of trialkyl aluminum propionate and aluminum trichloride in a mass ratio of 1: 1; the zirconium salt is a mixture of zirconium hydrogen phosphate, zirconium acetate and zirconium carbonate according to a mass ratio of 4:2: 1;
the alkoxy silane is a mixture of methyltrimethoxy silane and methyltriethoxy silane according to the mass ratio of 3: 1.
In the step c, the coupling agent is a mixture of KH560 and KH570 according to a mass ratio of 5: 2; the cross-linking agent is a mixture of dimethyl dimethoxy silane and phenyl triethoxy silane according to the mass ratio of 1: 2; the wet film volatilization control agent is a mixture of ethanol, ethylene glycol monoethyl ether propylene glycol dimethyl ether and tripropylene glycol monoethyl ether according to the mass ratio of 3:1: 1.
Example 3:
the preparation method of the high-hardness AR coating solution of the embodiment includes the following steps (the following components are all calculated by mass percent):
step a, synthesizing fine-particle-size self-crosslinking styrene-acrylic emulsion:
a1) adding 84% of deionized water into a reaction vessel, heating to 75 ℃ under the stirring state, adding 5% of emulsifier, stirring for 10min, then heating to 85 ℃, adding 0.5% of initiator, and continuing stirring for 2 min;
a2) after the temperature is stable, beginning to dropwise add 3% of mixed monomers, stopping dropwise adding after 20min, continuing dropwise adding 7% of mixed monomers after the solution has obvious blue light and the temperature is stable, and completing dropwise adding within 3 h;
a3) keeping the temperature at 85 ℃ for 2h, then heating to 95 ℃, adding 0.5% of initiator, and keeping the temperature for 1h to obtain the fine-particle-size self-crosslinking styrene-acrylic emulsion with the particle size of 90 nm.
B, preparing boron, aluminum and zirconium hybrid silica sol:
b1) adding a solvent and deionized water into a reaction vessel, adding boron salt, aluminum salt, zirconium salt and alkoxy silane under the condition of stirring, and heating to 60 ℃; in the step, the volume ratio of the solvent to the deionized water to the alkoxy silane is 8: 0.6: 1;
b2) after the temperature is stable, slowly dropwise adding the uniformly mixed solution of deionized water and the catalyst into a reaction vessel for 15min, keeping the temperature constant in the dropwise adding process, then carrying out heat preservation reaction for 2h, cooling to room temperature, and aging for 5d to obtain boron-aluminum-zirconium hybrid silica sol; in the step, the volume ratio of deionized water, catalyst and alkoxy silane is 0.8: 0.1: 1.
step c, preparing high-hardness AR coating liquid:
c1) adding 25% of boron-aluminum-zirconium hybrid silica sol into a reaction vessel, slowly adding 32% of fine-particle-size self-crosslinking styrene-acrylic emulsion into the reaction vessel under the condition of stirring at room temperature, continuously stirring for 10min, then respectively adding 0.1% of coupling agent and 1.2% of crosslinking agent, preserving heat for 2h at the temperature of 60 ℃, and cooling to room temperature to obtain a compound liquid;
c2) and under the condition of stirring at room temperature, adding 40% of a wet film volatilization control agent, 1.0% of a defoaming agent, 0.5% of a wear-resistant anti-scraping agent and 0.2% of a hardening agent into the compound liquid, and continuously stirring for 2.5 hours to obtain the high-hardness AR coating liquid.
In the embodiment, in the step a, the emulsifier is a mixture of cetyl trimethyl ammonium bromide and cetyl pyridine bromide in a mass ratio of 2: 1;
the initiator is a mixture of cumene hydroperoxide, tert-butyl hydroperoxide, benzoyl peroxide and dicumyl peroxide according to the mass ratio of 2:1:3: 1;
the mixed monomer is a mixture of maleic anhydride, methyl acrylate, N-hydroxymethyl acrylamide and dibutyl itaconate according to a mass ratio of 1:4:5: 1.
In the step b, the solvent is a mixture of methanol, n-butyl alcohol and dipropylene glycol methyl ether according to a mass ratio of 3:4: 1; the catalyst is a mixture of ethylamine and triethylamine according to a mass ratio of 6: 5.
The boron salt is a mixture of boron diboride trioxide, borax and aluminum diboride in a mass ratio of 3:1: 5; the aluminum salt is at least one of aluminum acetylacetonate; the zirconium salt is a mixture of zirconium ethoxide, zirconium propoxide, zirconium isopropoxide and zirconium acetylacetonate in a mass ratio of 1:1:3: 2;
the alkoxy silane is at least one of methyl triethoxysilane.
In the step c, the coupling agent is KH 560; the cross-linking agent is a mixture of methyl triethoxysilane and phenyl triethoxysilane in a mass ratio of 2: 1; the wet film volatilization control agent is a mixture of tripropylene glycol monomethyl ether and tripropylene glycol monoethyl ether according to a mass ratio of 3: 1.
Example 4:
the preparation method of the high-hardness AR coating solution of the embodiment includes the following steps (the following components are all calculated by mass percent):
step a, synthesizing fine-particle-size self-crosslinking styrene-acrylic emulsion:
a1) adding 76% of deionized water into a reaction vessel, heating to 65 ℃ under the stirring state, adding 8% of emulsifier, stirring for 15min, heating to 75 ℃, adding 1.2% of initiator, and continuing stirring for 5 min;
a2) after the temperature is stable, beginning to dropwise add 3.7% of mixed monomers, stopping dropwise adding after 17min, continuing to dropwise add 11% of mixed monomers after the solution has obvious blue light and the temperature is stable, and completing dropwise adding within 2.4 h;
a3) keeping the temperature at 75 ℃ for 5h, then heating to 85 ℃, adding 0.1% of initiator, and keeping the temperature for 3h to obtain the fine-particle-size self-crosslinking styrene-acrylic emulsion with the particle size of 60 nm.
B, preparing boron, aluminum and zirconium hybrid silica sol:
b1) adding a solvent and deionized water into a reaction vessel, adding boron salt, aluminum salt, zirconium salt and alkoxy silane under the condition of stirring, and heating to 50 ℃; in the step, the volume ratio of the solvent to the deionized water to the alkoxy silane is 5: 0.4: 1;
b2) after the temperature is stable, slowly dropwise adding the uniformly mixed solution of deionized water and the catalyst into a reaction vessel for 20min, keeping the temperature constant in the dropwise adding process, then carrying out heat preservation reaction for 4h, cooling to room temperature, and aging for 7d to obtain boron-aluminum-zirconium hybrid silica sol; in the step, the volume ratio of deionized water, catalyst and alkoxy silane is 0.4: 0.08: 1.
step c, preparing high-hardness AR coating liquid:
c1) adding 10% of boron-aluminum-zirconium hybrid silica sol into a reaction vessel, slowly adding 35% of fine-particle-size self-crosslinking styrene-acrylic emulsion into the reaction vessel under the condition of stirring at room temperature, continuously stirring for 30min, then respectively adding 1.5% of coupling agent and 0.5% of crosslinking agent, preserving heat for 10h at 25 ℃, and cooling to room temperature to obtain a compound liquid;
c2) and under the condition of stirring at room temperature, adding 52% of a wet film volatilization control agent into the compound solution, and continuously stirring for 2.2 hours to obtain the high-hardness AR coating solution.
In the embodiment, in the step a, the emulsifier is a mixture of potassium abietate, sodium butanedioic acid sulfonate and hexadecyl trimethyl ammonium bromide according to a mass ratio of 3:5: 1;
the initiator is a mixture of benzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide and peroxydicarbonate according to a mass ratio of 4:6:2: 3;
the mixed monomer is a mixture of styrene, acrylic acid, diethylene glycol dibutyl ester, glycidyl methacrylate and diallyl phthalate according to a mass ratio of 2:5:1:1: 3.
In the step b, the solvent is a mixture of ethylene glycol, glycerol, dipropylene glycol methyl ether, tripropylene glycol monomethyl ether and tripropylene glycol monoethyl ether according to a mass ratio of 3:1:1:1: 2; the catalyst is a mixture of hydrochloric acid and acetic acid according to the mass ratio of 1: 3;
the boron salt is a mixture of sodium tetraborate, potassium borohydride and boron trioxide according to the mass ratio of 1:1: 1; the aluminum salt is a mixture of aluminum nitrate, aluminum acetate and aluminum isopropoxide in a mass ratio of 5:3: 4; the zirconium salt is a mixture of zirconium chloride, zirconium carbonate, zirconium oxychloride and zirconium ethoxide according to a mass ratio of 1:6:1: 3;
the alkoxy silane is a mixture of tetraethoxy silane and methyl triethoxysilane according to the mass ratio of 1: 2.
In the step c, the coupling agent is a mixture of KH550 and KH570 in a mass ratio of 2:1: 2; the cross-linking agent is a mixture of methyltrimethoxysilane and dimethyldimethoxysilane according to the mass ratio of 3: 1; the wet film volatilization control agent is a mixture of deionized water isopropyl, glycerol dipropylene glycol methyl ether and propylene glycol dimethyl ether according to a mass ratio of 3:1: 1.
Although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted without departing from the true spirit and scope of the present invention.
Claims (9)
1. A high-hardness AR coating liquid is characterized in that: the material mainly comprises the following raw materials in percentage by mass:
10-25% of fine-particle-size self-crosslinking styrene-acrylic emulsion
15-35% of boron-aluminum-zirconium hybrid silica sol
0.1 to 1.5 percent of coupling agent
0.1 to 1.5 percent of cross-linking agent
The wet film volatilization control agent is 40% -60%;
wherein:
the fine-particle-size self-crosslinking styrene-acrylic emulsion is prepared from the following raw materials in percentage by mass:
53 to 84 percent of deionized water
5 to 15 percent of emulsifier
1 to 2 percent of initiator
10-30% of mixed monomer;
the boron-aluminum-zirconium hybrid silica sol is prepared from the following raw materials:
5-10 ml of solvent
0.4-1.6 ml of deionized water
0.01-0.1 g of boron salt
Aluminum salt 0.01-0.1 g
0.01-0.1 g of zirconium salt
0.01-0.1 ml of catalyst
1ml of alkoxy silane;
the particle size of the fine-particle-size self-crosslinking styrene-acrylic emulsion is 50-90 nm.
2. The high-hardness AR coating solution of claim 1, wherein: the high-hardness AR coating liquid also comprises an auxiliary agent, wherein the auxiliary agent is at least one of a leveling agent, a dispersing agent, a wetting agent, a defoaming agent, a wear-resistant anti-scraping agent and a hardening agent, and the total mass percentage of the auxiliary agent is 0.1-2%.
3. The high-hardness AR coating solution of claim 1, wherein: the emulsifier is at least one of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, potassium abietate, sodium butanedisulfonate, dodecyl ammonium chloride, hexadecyl trimethyl ammonium bromide, hexadecyl pyridine bromide, Span40, Span60, Span80, Tween40, Tween60 and Tween 80;
the initiator is at least one of ammonium persulfate, sodium persulfate, potassium persulfate, azobisisobutylamidine hydrochloride, azobisisobutylimidazoline hydrochloride, azobiscyanovaleric acid, azobisdiisopropylimidazoline, cumene hydroperoxide, tert-butyl hydroperoxide, benzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide and peroxydicarbonate;
the mixed monomer is formed by mixing styrene and at least one of acrylic acid, methacrylic acid, itaconic acid, maleic anhydride, methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, butyl acrylate, isooctyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, N-methylol acrylamide, dibutyl itaconate, isobornyl methacrylate, diethylene glycol dibutyl acrylate, glycidyl methacrylate and diallyl phthalate.
4. The high-hardness AR coating solution of claim 1, wherein: the solvent is at least one of methanol, ethanol, ethylene glycol, n-propanol, isopropanol, propylene glycol, glycerol, n-butanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, dipropylene glycol methyl ether, propylene glycol dimethyl ether, tripropylene glycol monomethyl ether and tripropylene glycol monoethyl ether;
the catalyst is one or more of hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, acetic acid, citric acid, oxalic acid, sodium hydroxide, potassium hydroxide, urea, ethylamine, ethylenediamine or triethylamine;
the boron salt is at least one of boric acid, sodium tetraborate, zinc borate, sodium borohydride, potassium borohydride, diboron trioxide, borax and aluminum diboride; the aluminum salt is at least one of aluminum nitrate, aluminum chloride, aluminum phosphate, aluminum formate, aluminum acetate, aluminum propionate, dialkyl aluminum chloride, monoalkyl aluminum dichloride, trialkyl aluminum trichloride, aluminum isopropoxide and aluminum acetylacetonate; the zirconium salt is at least one of zirconium dioxide, zirconium chloride, zirconium nitrate, zirconium hydrogen phosphate, zirconium acetate, zirconium carbonate, zirconium oxychloride, zirconium ethoxide, zirconium propoxide, zirconium isopropoxide and zirconium acetylacetonate;
the alkoxy silane is at least one of tetraethoxy silane, methyltrimethoxy silane and methyltriethoxy silane.
5. The high-hardness AR coating solution of claim 1, wherein: the coupling agent is at least one of KH550, KH560 and KH 570; the cross-linking agent is at least one of methyltrimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, dimethyldimethoxysilane and phenyltriethoxysilane; the wet film volatilization control agent is at least one of deionized water, methanol, ethanol, ethylene glycol, n-propanol, isopropanol, propylene glycol, glycerol, n-butanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, dipropylene glycol methyl ether, propylene glycol dimethyl ether, tripropylene glycol monomethyl ether and tripropylene glycol monoethyl ether.
6. The method for preparing high-hardness AR coating liquid according to claim 1, wherein the method comprises the following steps: the method comprises the following steps:
step a, synthesizing fine-particle-size self-crosslinking styrene-acrylic emulsion:
a1) adding deionized water into a reaction vessel according to the mass percentage, heating to 65-75 ℃ under the stirring state, adding an emulsifier, stirring for a certain time, then heating to 75-85 ℃, adding 0.5-1.5% of an initiator, and continuing to stir for a period of time;
a2) after the temperature is stable, beginning to dropwise add the mixed monomer with the mass percentage of 3-6%, stopping dropwise adding after 15-20 min, continuing dropwise adding the rest mixed monomer after the solution has obvious blue light and the temperature is stable, and completing dropwise adding within 1-3 h;
a3) preserving heat for 2-5 h at 75-85 ℃, then heating to 85-95 ℃, adding the rest initiator, and preserving heat for 1-3 h to obtain a fine-particle-size self-crosslinking styrene-acrylic emulsion;
b, preparing boron, aluminum and zirconium hybrid silica sol:
b1) adding a solvent and deionized water into a reaction vessel, adding boron salt, aluminum salt, zirconium salt and alkoxy silane under the condition of stirring, and heating to 25-60 ℃;
b2) after the temperature is stable, slowly dropwise adding the uniformly mixed solution of deionized water and a catalyst into a reaction vessel for 15-30 min, keeping the temperature constant in the dropwise adding process, then carrying out heat preservation reaction for 2-5 h, cooling to room temperature, and aging for 5-10 d to obtain boron-aluminum-zirconium hybrid silica sol;
step c, preparing high-hardness AR coating liquid:
c1) adding boron-aluminum-zirconium hybrid silica sol into a reaction vessel according to the mass percentage, slowly adding the fine-particle-size self-crosslinking styrene-acrylic emulsion into the reaction vessel under the condition of stirring at room temperature, continuously stirring for a period of time, then respectively adding a coupling agent and a crosslinking agent, preserving heat for 2-10 hours at the temperature of 25-60 ℃, and cooling to room temperature to obtain a compound liquid;
c2) and under the condition of stirring at room temperature, continuously stirring the wet film volatilization control agent in the compound solution for 1.5-2.5 h to obtain the high-hardness AR coating solution.
7. The method for preparing high-hardness AR coating liquid according to claim 6, wherein the method comprises the following steps: in the step a1, adding an emulsifier, and stirring for 10-15 min; the stirring time for adding the initiator is 2-5 min.
8. The method for preparing high-hardness AR coating liquid according to claim 6, wherein the method comprises the following steps: in the step b1, the volume ratio of the solvent to the deionized water to the alkoxy silane is (5-10): (0.2-0.8): 1;
in the step b2, the volume ratio of the deionized water to the catalyst to the alkoxysilane in the step b1 is (0.2-0.8): (0.01-0.1): 1.
9. the method for preparing high-hardness AR coating liquid according to claim 6, wherein the method comprises the following steps: and c1, slowly adding the fine-particle-size self-crosslinking styrene-acrylic emulsion into a reaction vessel, and continuously stirring for 10-30 min.
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