CN115404003A - Coating with antireflection, dustproof, antifogging and antistatic functions and preparation method thereof - Google Patents

Coating with antireflection, dustproof, antifogging and antistatic functions and preparation method thereof Download PDF

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CN115404003A
CN115404003A CN202211107563.1A CN202211107563A CN115404003A CN 115404003 A CN115404003 A CN 115404003A CN 202211107563 A CN202211107563 A CN 202211107563A CN 115404003 A CN115404003 A CN 115404003A
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optionally
coating
solution
acid
agent
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严国杭
张崇照
吴后胜
邬亚斌
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Xiamen Weiliang Optoelectronic Technology Co.,Ltd.
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Xiamen Winlight Optical Coating Technology Co ltd
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
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    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
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    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
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    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/006—Anti-reflective coatings
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    • C09D7/40—Additives
    • C09D7/65—Additives macromolecular
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
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    • C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
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Abstract

The invention relates to a coating with antireflection, dustproof, antifogging and antistatic functions and a preparation method thereof, belonging to the technical field of composite materials. The preparation method of the antireflection coating liquid comprises the following steps: s1, preparing a first solution from alkoxy silane, alcohol and water, adjusting the pH value of the first solution to 1-6, and carrying out hydrolytic condensation reaction for 5-20 h at the temperature of 30-100 ℃; s2, adding the nanoparticles with the hollow structure and a first solvent into the first solution subjected to the hydrolysis condensation reaction to prepare a second solution, and stirring the second solution at the temperature of 30-100 ℃ for 5-20 h; and S3, adding the antistatic agent, the antifogging agent, the auxiliary agent and the second solvent into the stirred second solution, and uniformly stirring to prepare the antireflection coating liquid. The antireflection coating liquid provided by the invention can realize a single-layer coating and simultaneously realize antistatic antireflection and antifogging effects in a thermosetting mode, and has a prospect of large-scale industrial production and application.

Description

Coating with antireflection, dustproof, antifogging and antistatic functions and preparation method thereof
Technical Field
The invention belongs to the field of composite materials, and particularly relates to a coating with antireflection, dustproof, antifogging and antistatic functions and a preparation method thereof.
Background
In the information age, various electronic products are developed vigorously, and optical plastics, glass and the like are widely applied to the electronic products. Optical plastic base materials with high mechanical strength and high toughness, such as Polycarbonate (PC), polyethylene terephthalate (PET), polymethyl methacrylate (PMMA), triacetyl cellulose (TAC) and the like, are widely applied to the fields of electronic components, display equipment, optical lenses, automobile central control panels, glass display cabinets, packaging materials and the like.
On one hand, the base materials have low light transmittance, only about 90% of light transmittance, and 8% of light can be reflected and lost, and on the other hand, the application of the base materials is limited due to the characteristics of easy generation of static electricity and easy dust absorption caused by friction.
Because the optical substrate is generally applied to electronic display screens and other devices, the optical substrate is required to have a higher antireflection effect in addition to the antistatic effect, and thus the antistatic functional coating coated on the surface of the optical substrate is required to have both antireflection and antistatic functions. However, when the method is applied to an environment with large temperature difference and humidity, water vapor is condensed on the surface of equipment at this time, and short-time fogging is formed. The light transmittance is reduced, the image is blurred, and glare is caused by diffuse reflection. Therefore, with various display visual windows, the requirements on the light transmittance of the base material, such as automobile central control panels, museum glass showcases, glasses and the like, are gradually improved. Other functions are added while maintaining high transmittance. Such as antistatic, dustproof, antifogging, self-cleaning, etc.
At present, a multi-layer functional coating with antireflection and antistatic capabilities can be coated on the surface of an optical substrate by adopting a sputtering method in a mixed atmosphere of argon and oxygen, but the process steps are complicated, the requirement on equipment is extremely high, the antifogging function is not realized, and the method is not suitable for large-scale industrial application; or a single-function coating with anti-reflection and antistatic capabilities is coated on the surface of the optical substrate by adopting a UV curing mode, but the process is limited by the thickness of the coating, namely, oxygen inhibition occurs when the thickness of the coating is 100-150 nm, so that the coating needs to be N 2 Can be completely cured in the atmosphere of (2), so that the method also has the problems of complex process steps and extremely high requirements on equipment, does not have an antifogging function, and is not suitable for large-scale industrial application. Or the multi-layer functional coating for antireflection and antifogging is made by adopting magnetron sputtering and other modes, the preparation methods of the coatings have the problems of complex process and the like, and the performances of antireflection, dust prevention, static resistance, antifogging and the like cannot be simultaneously met.
Disclosure of Invention
The invention aims to overcome the defects that the production process steps of the conventional antistatic, dustproof and antifogging functional coating are complicated, the requirement on equipment is extremely high, and the conventional antistatic, dustproof and antifogging functional coating is not suitable for large-scale industrial application, and provides a coating with antireflection, dustproof, antifogging and antistatic functions and a preparation method thereof.
In a first aspect, the preparation method of the antireflection coating solution provided by the invention adopts the following technical scheme:
a preparation method of an antireflection coating liquid specifically comprises the following steps:
s1, preparing a first solution from alkoxy silane, alcohol and water, adjusting the pH of the first solution to be 1-6, and carrying out hydrolytic condensation reaction for 5-20 h at the temperature of 30-100 ℃;
s2, adding the nanoparticles with the hollow structure and a first solvent into the first solution subjected to the hydrolysis condensation reaction to prepare a second solution, and stirring the second solution at the temperature of 30-100 ℃ for 5-20 h;
and S3, adding an antistatic agent, an antifogging agent, an auxiliary agent and a second solvent into the stirred second solution, and uniformly stirring to prepare the coating liquid.
By adopting the technical scheme, the continuous cross-linked network structure with porous closed pores is prepared by performing acid hydrolysis on alkoxysilane by utilizing a sol-gel method, then nano particles with a hollow structure, an antistatic agent and an antifogging agent are sequentially added into the nano particles, so that the coating liquid with high antireflection, antistatic, antifogging and dustproof effects is prepared, the coating liquid is coated on the surface of an optical substrate and is subjected to thermocuring to form a coating with high antireflection, antistatic, antifogging and dustproof effects.
Further, the structural general formula of the alkoxy silane is shown as formula 1:
Figure BDA0003842261920000031
R 1 is a substituted or unsubstituted monovalent hydrocarbon radical, R 2 Is C1-C3 alkyl, a =0, 1 or 2;
optionally, said R 1 Is one of alkyl, cycloalkyl, alkenyl, acryloxy, epoxy-substituted hydrocarbon, mercapto-substituted hydrocarbon or amino-substituted hydrocarbon;
more preferably, R is 1 Is one of methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, cyclopentyl, cyclohexyl, vinyl, allyl, gamma-methacryloxypropyl, gamma-glycidoxypropyl, 3,4-epoxycyclohexylethyl, gamma-mercaptopropyl or gamma-aminopropyl;
optionally, said R 2 Is one of methyl, ethyl or propyl;
more preferably, R is 2 Is methyl or ethyl;
optionally, in the step S1, the solid content of the reaction system of the hydrolysis condensation reaction is 8 to 13%;
optionally, in S1, the alkoxysilane is one or more of three kinds of alkoxysilanes, i.e., a =0, a =1, or a = 2;
preferably, the alkoxy silane is selected from one or more of silane coupling agent, methyl trimethoxy silane, gamma-glycidoxypropyl trimethoxy silane, vinyl trimethoxy silane, diethyl dimethoxy silane, gamma-aminopropyl triethoxy silane or gamma-mercaptopropyl methyl dimethoxy silane;
more preferably, the alkoxy silane is one or more of silane coupling agent, methyl trimethoxy silane or gamma-glycidyl ether oxygen propyl trimethoxy silane;
optionally, the pH is adjusted to 1-6 in S1 using an acid hydrolysis catalyst;
preferably, the acid hydrolysis catalyst is an organic acid and/or an inorganic acid;
more preferably, the acid hydrolysis catalyst is one or more of hydrochloric acid, nitric acid, acetic acid, propionic acid, oxalic acid, maleic acid, benzoic acid, malonic acid, glutaric acid, glycolic acid, and p-toluenesulfonic acid.
Further, the nano particles with hollow structures are nano silicon dioxide with hollow structures and/or nano titanium dioxide with hollow structures;
preferably, the nanoparticles with hollow structures are nano-silica with hollow structures;
optionally, the particle size of the hollow structured nanoparticles is 20-100 nm;
more preferably, the particle size of the hollow structured nanoparticles is 40 to 80nm.
Further, the antistatic agent is selected from one or more of conductive filler, cationic antistatic agent, anionic antistatic agent, zwitterionic antistatic agent or nonionic antistatic agent;
optionally, the conductive filler is selected from carbon black, graphite, nano silver, nano ATO, aluminum-doped zinc oxide AZO, and nano TiO 2 Or MTO;
optionally, the cationic antistatic agent is selected from trialkyl ammonium salts and/or tetraalkyl ammonium salts;
optionally, the anionic antistatic agent is selected from one or more of alkyl phosphate, alkyl benzene sulfonate, alkyl sulfonate or alkyl sulfate;
optionally, the zwitterionic antistatic agent is selected from one or more of alkyl betaine, imidazoline or alkyl dicarboxymethylammonium glycolide;
optionally, the nonionic antistatic agent is selected from one or more of polyoxyethylene fatty ether, polyoxyethylene alkyl phenyl ether or glycerin fatty acid ester.
Further, the antifogging agent is selected from a nonionic surfactant, an anionic surfactant or a cationic surfactant;
optionally, the nonionic surfactant is one or more of glycerol ester, polyglycerol ester, sorbitan ester, ethoxylated nonyl phenol, ethoxylated alcohol or carboxylated polyvinyl alcohol;
optionally, the anionic surfactant is an alkyl sulfonate and/or alkyl carboxylate;
optionally, the cationic surfactant is fluorocarbon cationic surfactant, hexadecyl trimethyl quaternary ammonium bromide, octadecyl dimethyl benzyl quaternary ammonium chloride.
By adopting the technical scheme, the antifogging agent and the antistatic agent can form orientation arrangement on the coating interface, the hydrophilic group is arranged towards one side of the air, and a layer of film with the conductive capability is formed by hydrogen bonds and moisture in the air, so that static electricity can be dissipated quickly, dust in the air can not be adsorbed, the ultrathin transparent film does not scatter and glare incident light, and the purposes of static resistance, dust prevention and fog prevention are achieved.
Further, the first solvent and the second solvent are independently selected from one or more of alcohols, ethers, esters or ketones;
optionally, the auxiliary agent is selected from one or more of a leveling agent, a defoaming agent or a wetting agent.
Furthermore, the adding amount ratio of the alkoxy silane and the water in the S1 is that the molar ratio of hydroxyl in the water to siloxane SiOR2 in the alkoxy silane is (1-2): 1;
the input mass ratio of the nanoparticles with the hollow structure to the alkoxy silane is (1-5): (1-1.2);
the solid content of the antireflection coating liquid in the S3 is 3-6%, wherein the concentration of the antistatic agent is 0.09-0.80 wt%, the concentration of the antifogging agent is 0.09-0.80 wt%, and the concentration of the auxiliary agent is 0.009-0.09 wt%.
In a second aspect, the invention provides the antireflection coating liquid prepared by any one of the above preparation methods.
In a third aspect, the anti-fog, anti-dust and anti-static film with the anti-reflection function adopts the following technical scheme:
a dustproof, antifogging and antistatic film with an antireflection film function is prepared by the antireflection coating liquid prepared by the preparation method of any one of the antireflection coating liquids and/or the antireflection coating liquid through thermocuring at 90-100 ℃;
optionally, the coating has a continuous cross-linked network of porous closed pores;
optionally, the thickness of the coating is 100 to 150nm;
optionally, the coating has a light transmittance of 97.12-99.12% and a surface impedance of 10 7 -10 10 ；
Optionally, the coating has an adhesion of 5B.
Optionally, the antifogging property is 30s in water vapor at 60 ℃, and the coating still keeps transparent;
optionally, the reflectivity is 0.12-0.33%.
By adopting the technical scheme, the coating can be used for products such as PET films, glass showcases, electronic equipment with display screens, electronic devices, packaging materials and the like.
In a fourth aspect, the dustproof, antifogging and antistatic optical product provided by the invention adopts the following technical scheme:
the anti-static, dustproof and anti-fog optical product is characterized in that the anti-static, anti-fog and anti-fog coating with the anti-reflection function is arranged on the surface of the optical product.
Has the advantages that:
(1) The coating solution is prepared by a sol-gel method, is coated on the surface of an optical substrate, can be completely cured to form a dustproof, antifogging, antistatic and antireflection coating under the condition of thermal curing at 90-100 ℃, has simple preparation conditions and process and low requirements on equipment, and is suitable for large-scale industrial production of antistatic, dustproof and antifogging functional coatings;
(2) According to the invention, a specific alkoxy silane film-forming substance is used for preparing organic silicon resin with a continuous cross-linked network structure by adopting an acid hydrolysis mode, nano particles with a hollow structure, an antistatic agent and an antifogging agent are sequentially added into the organic silicon resin, the organic silicon resin can be completely cured only at 90-100 ℃ to form a coating with a porous structure, and then the antifogging and dustproof coating with low refractive index and low surface impedance is prepared;
(3) In addition, the coating provided by the invention has better binding force with the optical base material, the adhesive force grade is 5B, the falling-off of the coating in the using process can be reduced, and the service life of the coating is further prolonged.
Drawings
In order to illustrate the technical solution of the present invention more clearly, the drawings will be briefly described below, and it is apparent that the drawings in the following description relate only to some embodiments of the present invention and are not intended to limit the present invention.
FIG. 1 is an SEM image of a coating layer coated on a surface of a PC optical plastic substrate provided in example 1 of the present invention;
FIG. 2 is a graph showing the transmittance of a coating layer coated on the surface of a PC optical plastic substrate according to example 1 of the present invention;
FIG. 3 is a graph of the reflectance of a coating applied to the surface of a PC optical plastic substrate provided in example 1 of the present invention.
Detailed Description
Preferred embodiments of the present invention will be described in more detail below. While the following describes preferred embodiments of the present invention, it should be understood that the present invention may be embodied in various forms and should not be limited by the embodiments set forth herein. The examples do not specify particular techniques or conditions, and are performed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available. In the following examples, "%" means weight percent, unless otherwise specified.
"solids content", as a percentage by weight after removal of solvent and water; the solid content of the reaction system of the hydrolysis condensation reaction is the mass percentage of the reaction system with the original reaction system after the organic solvent and water are removed, and the solid content of the antireflection coating liquid is the mass percentage of the antireflection coating liquid with the original reaction system after the organic solvent and water are removed.
The reagents and sources used in the present invention are as follows:
TEOS (tetraethyl orthosilicate) (New Material Ltd of Han, hubei, inc., product number JH-T28);
methyltrimethoxysilane (Hubei Jiangsan New materials Co., ltd., product number JH-N311);
gamma-glycidyl ether oxypropyltrimethoxysilane (New Hubanhan New materials GmbH, hubei, cat. JH-0187);
vinyltrimethoxysilane (New materials, inc. of New blue sky, hubei, cat. No. LT-171);
diethoxydimethylsilane (Shandongyuan brocade new materials Co., ltd., product No. YJ-1102);
aminopropyltriethoxysilane (New materials, inc. of New blue sky, hubei, cat # LT-550);
gamma-mercaptopropylmethyldimethoxysilane (Hubei Chengfeng chemical Co., ltd., product No. LM-582).
The application provides a preparation method of an antireflection coating liquid, which specifically comprises the following steps:
s1, preparing a first solution from alkoxy silane, alcohol and water, adjusting the pH of the first solution to be 1-6, and carrying out hydrolytic condensation reaction for 5-20 h at the temperature of 30-100 ℃;
s2, adding the nanoparticles with the hollow structure and a first solvent into the first solution subjected to the hydrolysis condensation reaction to prepare a second solution, and stirring the second solution at the temperature of 30-100 ℃ for 5-20 h;
and S3, adding an antifogging agent, an antistatic agent, an auxiliary agent and a second solvent into the stirred second solution, and uniformly stirring to prepare the coating liquid.
According to the invention, the antifogging agent and the antistatic agent can form a layer of film with conductivity and antifogging capability on the surface of the organic silicon resin obtained by hydrolyzing alkoxy silane with acid, and the conductivity cannot be influenced by the addition of the nano particles with hollow structures.
In many embodiments, the alkoxysilane has a general structural formula as shown in formula 1:
Figure BDA0003842261920000091
R 1 is a substituted or unsubstituted monovalent hydrocarbon radical, R 2 Is a C1-C3 alkyl group, a =0, 1 or 2;
optionally, said R 1 Is one of alkyl, cycloalkyl, alkenyl, acryloxy, epoxy-substituted hydrocarbon, mercapto-substituted hydrocarbon or amino-substituted hydrocarbon;
more preferably, R is 1 Is one of methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, cyclopentyl, cyclohexyl, vinyl, allyl, gamma-methacryloxypropyl, gamma-glycidoxypropyl, 3,4-epoxycyclohexylethyl, gamma-mercaptopropyl or gamma-aminopropyl;
optionally, said R 2 Is one of methyl, ethyl or propyl;
more preferably, R is 2 Is methyl or ethyl;
optionally, in the step S1, the solid content of the reaction system of the hydrolysis condensation reaction is 8 to 13%;
optionally, in S1, the alkoxysilane is one or more of three alkoxysilanes, a =0, a =1, or a = 2;
preferably, the alkoxy silane is selected from one or more of silane coupling agent, methyl trimethoxy silane, gamma-glycidoxypropyl trimethoxy silane, vinyl trimethoxy silane, diethyl dimethoxy silane, gamma-aminopropyl triethoxy silane or gamma-mercapto propyl methyl dimethoxy silane;
more preferably, the alkoxy silane is one or more of silane coupling agent, methyl trimethoxy silane or gamma-glycidyl ether oxygen propyl trimethoxy silane;
optionally, the pH is adjusted to 1-6 in S1 using an acid hydrolysis catalyst;
preferably, the acid hydrolysis catalyst is an organic acid and/or an inorganic acid;
more preferably, the acid hydrolysis catalyst is one or more of hydrochloric acid, nitric acid, acetic acid, propionic acid, oxalic acid, maleic acid, benzoic acid, malonic acid, glutaric acid, glycolic acid, and p-toluenesulfonic acid.
In the invention, the molar ratio of the alkoxy silane to the alcohol is controlled within a certain range, so that the antistatic agent can better form a film with conductive capability in the organic silicon resin prepared by acid hydrolysis.
In many embodiments, the hollow structured nanoparticles are nanosilica with hollow structures and/or nanosilica with hollow structures;
preferably, the nanoparticles with hollow structures are nano-silica with hollow structures;
optionally, the particle size of the hollow structured nanoparticles is 20-100 nm;
more preferably, the particle size of the hollow structured nanoparticles is 40 to 80nm.
According to the invention, the nano particles with hollow structures are added into the organic silicon resin formed by hydrolyzing the alkoxysilane acid, so that the coating liquid can form a coating with a porous structure after being cured at low temperature, the refractive index of the coating is further reduced, and the coating has an excellent antireflection effect.
In many embodiments, the antistatic agent is selected from one or more of a conductive filler, a cationic antistatic agent, an anionic antistatic agent, a zwitterionic antistatic agent, or a nonionic antistatic agent;
optionally, the conductive filler is selected from one or more of carbon black, graphite, nano silver, nano ATO, aluminum-doped zinc oxide AZO, nano TiO2 or MTO;
optionally, the cationic antistatic agent is selected from trialkyl ammonium salts and/or tetraalkyl ammonium salts;
optionally, the anionic antistatic agent is selected from one or more of alkyl phosphate, alkyl benzene sulfonate, alkyl sulfonate or alkyl sulfate;
optionally, the zwitterionic antistatic agent is selected from one or more of alkyl betaine, imidazoline or alkyl dicarboxymethyl ammonium ethyl lactone;
optionally, the nonionic antistatic agent is selected from one or more of polyoxyethylene fatty ether, polyoxyethylene alkyl phenyl ether or glycerin fatty acid ester.
In many embodiments, the antifog agent is selected from a nonionic surfactant, an anionic surfactant, or a cationic surfactant;
optionally, the nonionic surfactant is one or more of glycerol ester, polyglycerol ester, sorbitan ester, ethoxylated nonyl phenol, ethoxylated alcohol or carboxylated polyvinyl alcohol;
optionally, the anionic surfactant is an alkyl sulfonate and/or alkyl carboxylate;
optionally, the cationic surfactant is a first order alkali metal cation salt.
In the invention, the first-order alkali metal cation salt is one or more of fluorocarbon cationic active agent, hexadecyl trimethyl quaternary ammonium bromide or octadecyl dimethyl benzyl quaternary ammonium chloride.
In many embodiments, the solvent is selected from one or more of alcohols, ethers, esters, or ketones;
optionally, the auxiliary agent is selected from one or more of a leveling agent, a defoaming agent or a wetting agent.
In the invention, the alcohol can be one or more of methanol, ethanol, isopropanol, n-butanol or isobutanol;
the ethers may be one or more of ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether or propylene glycol butyl ether;
the esters can be one or more of methyl acetate, ethyl acetate, propyl acetate and isobutyl acetate;
the ketone may be one or more of acetone, butanone, methyl butanone, or methyl isobutyl ketone.
In many embodiments, the alkoxysilane and water in S1 are added in such a ratio that the hydroxyl groups in water are present in the siloxane SiOR in the alkoxysilane 2 The molar ratio of (1-2): 1;
the mass ratio of the using amount of the nanoparticles with the hollow structures in the S2 to the alkoxysilane in the S1 is (1-5): (1-1.2);
the solid content of the antireflection coating liquid in the S3 is 3-6%, wherein the concentration of the antistatic agent is 0.09-0.80 wt%, the concentration of the antifogging agent is 0.09-0.80 wt%, and the concentration of the auxiliary agent is 0.009-0.09 wt%.
The application also provides the antireflection coating liquid prepared by the preparation method of the antireflection coating liquid.
The application also provides a dustproof, antifogging and antistatic coating with an antireflection function, which is prepared by the preparation method of any one of the antireflection coating liquids and/or the antireflection coating liquid through thermocuring at 90-100 ℃;
optionally, the coating has a continuous cross-linked network of porous closed pores;
optionally, the thickness of the coating is 100-150 nm;
optionally, the coating has a light transmittance of 97.12-99.12% and a surface impedance of 10 7 -10 10 Ω；
Optionally, the coating has an adhesion rating of 5B;
optionally, the coating is in water vapor at 60 ℃ for 30s, and the coating still keeps transparent;
optionally, the coating has a reflectivity of 0.12 to 0.33%.
The application also provides an antistatic optical plastic product, the optical plastic product is provided with the above on the surface the dustproof, antifogging and antistatic coating with the antireflection function.
In the present invention, the optical plastic product may be made of one of carbonate (PC), polyethylene terephthalate (PET), polymethyl methacrylate (PMMA), and triacetyl cellulose (TAC).
The hollow-structured nano-silica particles used in the following examples were prepared according to the following methods:
0.3g of PAA (polyacrylic acid Mw 3000) was added to 8ml of concentrated ammonia water and stirred until completely dissolved. Then poured into 200ml of absolute ethanol and the solution was mixed well with magnetic stirring. To the mixed solution was slowly added dropwise 0.3ml of TEOS (tetraethylorthosilicate) every 1hr while stirring. The solution was added dropwise 5 times in total. After all TEOS (tetraethyl orthosilicate) is added dropwise, stirring is continued for 10hr. And finally, treating the hollow silica in a centrifugal mode. The solution is centrifugally washed by absolute ethyl alcohol for 3 times and then by deionized water for 2 times. A solid was obtained. After drying, adding into water to obtain the hollow nano-silica particles with solid content of 20wt% and average particle size of 50 nm.
Example 1. Anti-reflection coating solution and dustproof, antifogging, antistatic coating
The embodiment provides an antireflection coating solution, which is prepared by the following steps:
s1, adding 117.19g of silane coupling agent, 136.78g of methyltrimethoxysilane, 95.47g of gamma-glycidoxypropyltrimethoxysilane, 1076.14g of isopropyl ketone, 29.30g of acetic acid and 232.62g of water into a reactor to prepare a first solution, wherein the pH of the first solution is 3, and the first solution is stirred for 7 hours at the temperature of 100 ℃;
s2, slowly adding 843.75g of hollow-structure nano-silica particles and 843.75g of propylene glycol into the first solution subjected to the hydrolysis condensation reaction to prepare a second solution, and stirring and reacting the second solution at 30 ℃ for 20 hours;
and S3, adding 4162.5g of isobutanol, 810g of ethylene glycol butyl ether, 8.35g of a leveling agent (ByK 333), 16.70g of sodium alkyl sulfonate and 16.70g of nano silver into the stirred and reacted second solution, and uniformly stirring to prepare the antireflection coating liquid.
Wherein, the antireflection coating liquid contains 1.99wt% of hollow nano silicon dioxide, 0.1973wt% of nano silver and 0.1973wt% of sodium alkyl sulfonate.
And (3) coating the antireflection coating liquid on a PC (polycarbonate) optical plastic substrate, and curing at 100 ℃ for 30min to prepare a coating with the thickness of 100nm, wherein an SEM (scanning electron microscope) picture of the coating is shown in figure 1, and a coating layer is formed on the PC optical plastic substrate and has a continuous cross-linked network structure with porous closed pores. First, the transmittance test of the PC optical plastic substrate and the PC optical plastic substrate with the coating layer bonded thereon resulted in a transmittance curve as shown in fig. 2, and it can be seen from fig. 2 that: compared with the PC optical plastic base material, the light transmittance of the PC optical plastic base material combined with the coating is remarkably improved, which shows that the coating has excellent antireflection performance; secondly, the reflectivity of the PC optical plastic substrate combined with the coating is tested, and the experimental result is shown in FIG. 3, the reflectivity is low in the waveband of 400-760 nm, and the excellent antireflection performance of the coating can be further illustrated.
Example 2. Antireflection coating solution and dustproof, antifogging, antistatic coating
The embodiment provides an antireflection coating solution, which is prepared by the following steps:
s1, 157.86g of vinyltrimethoxysilane, 168.74g of diethoxydimethylsilane, 1148.96g of ethanol, 15g of 1mol/L hydrochloric acid and 196.94g of water are added into a reactor to prepare a first solution, the pH value of the first solution is 1, and the first solution is stirred for 7 hours at the temperature of 80 ℃;
s2, slowly adding 361.61g of hollow-structure nano-silica particles and 360.69g of butanone into the first solution subjected to hydrolysis condensation reaction to prepare a second solution, and stirring and reacting the second solution at 80 ℃ for 15 hours;
and S3, adding 4417.97g of ethylene glycol butyl ether, 1204.9g of ethyl acetate, 8.03g of a leveling agent (ByK 346) and 24.10g of nano ATO and glycerol ester into the stirred and reacted second solution, and uniformly stirring to prepare the coating liquid.
Wherein, the antireflection coating liquid contains 0.8968wt% of hollow nano-silica, 0.7498wt% of nano ATO and 0.7498wt% of glycerol ester.
And (3) coating the antireflection coating liquid on a PET (polyethylene terephthalate) optical plastic substrate, and curing for 30min at 100 ℃ to prepare a coating with the thickness of 100nm.
Example 3 antireflection coating solution and dustproof, antifogging, antistatic coating
The embodiment provides an antireflection coating solution, which is prepared by the following steps:
s1, adding 585.94g of silane coupling agent, 676.41g of methanol, 20g of glycolic acid and 405.15g of water into a reactor to prepare a first solution, wherein the pH of the first solution is 3, and the first solution is stirred for 5 hours at the temperature of 50 ℃;
s2, slowly adding 3375g of hollow nano-silica particles and 3375g of isopropanol into the first solution subjected to the hydrolysis condensation reaction to prepare a second solution, and stirring the second solution at 90 ℃ for reaction for 10 hours;
s3, adding 6750g of methyl acetate, 1687.5g of propylene glycol methyl ether, 1.69g of a flatting agent (ByK 348) and 12.65g of aluminum-doped zinc oxide AZO into the second solution subjected to the stirring reaction, and uniformly stirring to prepare the coating liquid.
Wherein, the antireflection coating liquid contains 4.99wt% of nano silicon dioxide with a hollow structure, 0.0936wt% of aluminum-doped zinc oxide AZO and 0.0936wt% of hexadecyl trimethyl ammonium bromide.
And (3) coating the antireflection coating liquid on a PET (polyethylene terephthalate) optical plastic substrate, and curing for 30min at 100 ℃ to prepare a coating with the thickness of 100nm.
Example 4. Antireflective coating solution and dustproof, antifogging, antistatic coating this example provides an antireflective coating solution, prepared by the following steps:
s1, adding 238.68g of gamma-glycidoxypropyltrimethoxysilane, 1309.75g of ethanol, 30g of 1mol/L acetic acid and 109.07g of water into a reactor to prepare a first solution, wherein the pH of the first solution is 3, and the first solution is stirred for 5 hours at the temperature of 30 ℃;
s2, slowly adding 1265.65g of hollow-structure nano-silica particles and 1265.65g of ethylene glycol monoethyl ether into the first solution subjected to the hydrolysis condensation reaction to prepare a second solution, and stirring and reacting the second solution at 30 ℃ for 5 hours;
s3, adding 5273.5g of acetone, 1054.7g of ethanol, 10.547g of a leveling agent (ByK 333), 63.28g of alkyl dicarboxymethylammonium acetolide and 63.28g of ethoxylated nonylphenol into the stirred and reacted second solution, and uniformly stirring to prepare the coating liquid.
Wherein, the antireflection coating liquid contains 2.38wt% of nano silicon dioxide with a hollow structure, 3238 wt% of alkyl dicarboxyl methyl ammonium ethyl lactone and 3262 wt% of ethoxylated nonyl phenol.
And (3) coating the antireflection coating liquid on a PET (polyethylene terephthalate) optical plastic substrate, and curing for 30min at 100 ℃ to prepare a coating with the thickness of 100nm.
Example 5 antireflection coating solution and dustproof, antifogging, antistatic coating
The embodiment provides an antireflection coating solution, which is prepared by the following steps:
s1, adding 72.99g of aminopropyltriethoxysilane, 68.39g of methyltrimethoxysilane, 135.92g of gamma-mercaptopropylmethyldimethoxysilane, 1246.16g of methanol, 20g of oxalic acid and 144.04g of water into a reactor to prepare a first solution, wherein the pH of the first solution is 2, and the first solution is stirred for 7 hours at the temperature of 60 ℃;
s2, slowly adding 843.75g of hollow-structure nano-silica particles and 843.75g of acetone into the first solution subjected to the hydrolysis condensation reaction to prepare a second solution, and stirring the second solution at 100 ℃ for reaction for 10 hours;
s3, adding 6750g of ethanol, 1125g of propylene glycol monomethyl ether, 11.25g of a leveling agent (bike BYK 346), 33.75g of nano ATO and 33.75g of sorbitan ester into the stirred and reacted second solution, and uniformly stirring to prepare the antireflection coating liquid.
Wherein the antireflection coating liquid contains 1.49wt% of nano silicon dioxide with a hollow structure, 0.2988wt% of nano ATO, and 0.2988wt% of sorbitan ester.
And (3) coating the antireflection coating liquid on a TAC optical plastic substrate, and curing for 30min at 100 ℃ to prepare a coating with the thickness of 100nm.
Example 6 antireflection coating solution and dustproof, antifogging, antistatic coating
The embodiment provides an antireflection coating solution, which is prepared by the following steps:
s1, adding 292.97g of silane coupling agent, 157.95g of vinyltrimethoxysilane, 1067.79g of isopropanol, 10g of p-toluenesulfonic acid and 158.79g of water into a reactor to prepare a first solution, wherein the pH of the first solution is 1, and the first solution is stirred for 10 hours at the temperature of 50 ℃;
s2, slowly adding 843.75g of hollow nano-silica particles and 843.75g of isobutanol into the first solution subjected to the hydrolysis condensation reaction to prepare a second solution, and stirring and reacting the second solution at 50 ℃ for 5 hours;
and S3, adding 2700g of ethyl acetate, 675g of ethanol, 6.75g of a leveling agent (ByK 346) and 16.875g of aluminum-doped zinc oxide AZO and 16.875g of sorbitan ester into the stirred and reacted second solution, and uniformly stirring to prepare the antireflection coating liquid.
Wherein, the antireflection coating liquid contains 2.49t percent of nano silicon dioxide with a hollow structure, 0.2491wt percent of aluminum-doped zinc oxide AZO and 0.2491wt percent of sorbitan ester.
And (3) coating the antireflection coating liquid on a PMMA optical plastic substrate, and curing for 30min at 100 ℃ to prepare a coating with the thickness of 100nm.
Example 7 antireflection coating solution and dustproof, antifogging, antistatic coating
This example is different from example 1 in that the first solution was stirred at 30 ℃ for 20 hours, the particle diameter of the nano-silica particles having a hollow structure was 100nm, the thickness of the antistatic film was 150nm, and the antifogging agent was carboxylated polyvinyl alcohol.
Example 8 anti-reflective coating solution and anti-dust, anti-fog, anti-static coating
This example is different from example 1 in that 117.19g of silane coupling agent, 136.78g of methyltrimethoxysilane, 95.47g of gamma-glycidoxypropyltrimethoxysilane, 1076.14g of isopropyl ketone, 29.30g of propionic acid and 232.62g of water are taken in S1 and added into a reactor to prepare a first solution, and the hollow structured nano-titania with a hollow structure, which is added into the first solution after hydrolysis condensation reaction, has a particle size of 100nm.
Example 9 antireflection coating solution and dustproof, antifogging, antistatic coating
The difference between this example and example 1 is that 117.19g of silane coupling agent, 136.78g of methyltrimethoxysilane, 95.47g of gamma-glycidoxypropyltrimethoxysilane, 1076.14g of isopropyl ketone, 29.30g of maleic acid and 232.62g of water are taken in S1 and added into a reactor to prepare a first solution, and the hollow-structured nanoparticles added into the first solution after hydrolysis and condensation reaction are hollow-structured nano-titania with a particle size of 20nm.
Example 10 antireflection coating solution and dustproof, antifogging, antistatic coating
This example differs from example 1 in that 117.19g of silane coupling agent, 136.78g of methyltrimethoxysilane, 95.47g of gamma-glycidoxypropyltrimethoxysilane, 1076.14g of isopropyl ketone, 29.30g of benzoic acid, and 232.62g of water were charged into a reactor in S1 to prepare a first solution.
Example 11 anti-reflective coating solution and anti-dust, anti-fog, anti-static coating
This example differs from example 1 in that 117.19g of silane coupling agent, 136.78g of methyltrimethoxysilane, 95.47g of gamma-glycidoxypropyltrimethoxysilane, 1076.14g of isopropyl ketone, 29.30g of malonic acid, and 232.62g of water were taken in S1 and a first solution was prepared.
Example 12 anti-reflective coating solution and anti-dust, anti-fog, anti-static coating
This example differs from example 1 in that 117.19g of silane coupling agent, 136.78g of methyltrimethoxysilane, 95.47g of gamma-glycidoxypropyltrimethoxysilane, 1076.14g of isopropyl ketone, 29.30g of glutaric acid, and 232.62g of water were charged into a reactor in S1 to prepare a first solution.
Comparative example 1 Effect of alkoxysilane hydrolysis conditions on coating conductivity
The comparative example provides an antistatic coating liquid, which is prepared by the following steps:
s1, adding 157.86g of vinyltrimethoxysilane, 168.74g of diethoxydimethylsilane, 1148.96g of ethanol, 15g of 1mol/L sodium hydroxide and 196.94g of water into a reactor to prepare a first solution, wherein the pH of the first solution is 12, and the first solution is stirred for 7 hours at the temperature of 80 ℃;
s2, slowly adding 361.61g of hollow-structure nano-silica particles and 360.69g of butanone into the first solution subjected to hydrolysis condensation reaction to prepare a second solution, and stirring and reacting the second solution at 80 ℃ for 15 hours;
s3, adding 4417.97g of ethylene glycol butyl ether, 1204.9g of ethyl acetate, 8.03g of a leveling agent (ByK 346) and 24.10g of nano ATO and 24.10g of glycerol ester into the stirred and reacted second solution, and uniformly stirring to prepare the antistatic film plating liquid.
Wherein, the antistatic coating liquid contains 0.8968wt% of hollow nano-silica, 0.7498wt% of nano ATO and 0.7498wt% of glycerol ester.
And (3) coating the antireflection coating liquid on a PET (polyethylene terephthalate) optical plastic substrate, and curing for 30min at 100 ℃ to prepare a coating with the thickness of 100nm.
Examples of the experiments.
The test methods used below included:
1. light transmittance: the transmittance of light in a wavelength band of 380 to 780nm was measured using a TMS transmittance meter, and the transmittance of the optical plastic substrates with the antistatic film provided in examples 1 to 6 and comparative example 1 was evaluated using a gain evaluation method: and the gain delta T = tau after coating-tau before coating, wherein tau is the effective transmittance of the optical plastic substrate.
2. Surface resistance: the antistatic films provided in examples 1 to 6 and comparative example 1 were tested for surface resistance using a TRACK MODEL-100 surface resistance tester.
3. Water contact angle: SDC-200S contact Angle measuring apparatus, a test was performed after dropping a drop of water on the surface of the antistatic film provided in examples 1 to 6 and comparative example 1 for 5S using deionized water, and three points at intervals of 1cm were taken for each sample and measured for 6 readings, and the average value was taken.
4. And (3) testing the adhesive force: 100 lattices each having a length and a width of 1mm were scribed on the optical plastic substrates to which the antistatic films were bonded, provided in examples 1 to 6 and comparative example 1, using a hundred-grid test knife, attached to the positions of the hundred-grid scratches with a 3M 810# tape, the edge of the tape was lifted, and the tape was rapidly peeled off in a direction perpendicular to the film surface at 90 degrees, and repeated 3 times. The degree of peel-off of the surface coating was tested and expressed as 1B to 5B.
5. Haze: the optical plastic substrates provided in examples 1 to 6 and comparative example 1, to which the antistatic film was bonded, were tested for haze using a color haze meter CS-720, and three points 2cm apart were taken for each sample, and 6 readings were taken and averaged.
6. Antifogging test: the sample was placed over a 60 ℃ water bath, exposed to steam for 30 seconds, and then the coating was visually inspected for clarity and passed if the coating remained clear. If the coating is hazy or hazy, it is rejected.
7. Reflectance & film thickness test: the coatings were tested for film thickness and reflectivity using a FILMETRICS film thickness gauge. Three points were taken for each sample and the average was taken.
The results of performance tests on the antistatic films provided in examples 1 to 6 and comparative example 1 are shown in table 1:
TABLE 1 Performance test results of antistatic films
Figure BDA0003842261920000211
As can be seen from Table 1, the antistatic films prepared in examples 1 to 6 all had better light transmittanceSurface impedance is 10 7 -10 10 In addition, the adhesive force test shows that the adhesive force is 5B, no one lattice of the hundred lattices falls off, and the antistatic film has good adhesive force with the optical plastic base material; wherein the antistatic film prepared by the method provided in example 1 had a surface impedance of 10 7 Omega, the antistatic ability is stronger, and the luminousness reaches up to 99.12%, and the reflectivity is as low as 0.12%, and the coating has excellent dustproof, antifogging, antistatic ability and high antireflection effect simultaneously.
Example 2 differs from comparative example 1 only in that the hydrolysis conditions of alkoxysilane are different, i.e. the hydrolysis conditions of example 2 are acidic, while the hydrolysis conditions of comparative example 1 are basic, but the two produced coatings have a large difference in performance, comparative example 1 provides a coating with surface impedance four orders of magnitude greater than that of example 2, the antistatic ability of example 2 is significantly better than that of comparative example 1, and likewise, the hydrolysis conditions of alkoxysilane have a large influence on the antifogging ability of the produced coating, and the coating of comparative example 1 does not have antifogging ability.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are all within the protection scope of the present invention.
It should be noted that the various features described in the above embodiments may be combined in any suitable manner without departing from the scope of the invention. The invention is not described in detail in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.

Claims (10)

1. The preparation method of the antireflection coating liquid is characterized by comprising the following steps:
s1, preparing a first solution from alkoxy silane, alcohol and water, adjusting the pH of the first solution to be 1-6, and carrying out hydrolytic condensation reaction for 5-20 h at the temperature of 30-100 ℃;
s2, adding the nanoparticles with the hollow structure and a first solvent into the first solution subjected to the hydrolysis condensation reaction to prepare a second solution, and stirring the second solution at the temperature of 30-100 ℃ for 5-20 h;
and S3, adding an antistatic agent, an antifogging agent, an auxiliary agent and a second solvent into the stirred second solution, and uniformly stirring to prepare the coating liquid.
2. The method for preparing the anti-reflection coating liquid according to claim 1, wherein the structural general formula of the alkoxysilane is as shown in formula 1:
Figure FDA0003842261910000011
R 1 is a substituted or unsubstituted monovalent hydrocarbon radical, R 2 Is a C1-C3 alkyl group, a =0, 1 or 2;
optionally, said R 1 Is one of alkyl, cycloalkyl, alkenyl, acryloxy, epoxy-substituted hydrocarbon, mercapto-substituted hydrocarbon or amino-substituted hydrocarbon;
more preferably, R is 1 Is one of methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, cyclopentyl, cyclohexyl, vinyl, allyl, gamma-methacryloxypropyl, gamma-glycidoxypropyl, 3,4-epoxycyclohexylethyl, gamma-mercaptopropyl or gamma-aminopropyl;
optionally, said R 2 Is one of methyl, ethyl or propyl;
more preferably, R is 2 Is methyl or ethyl;
optionally, in the step S1, the solid content of the reaction system of the hydrolysis condensation reaction is 8 to 13%;
optionally, in S1, the alkoxysilane is one or more of three alkoxysilanes, a =0, a =1, or a = 2;
preferably, the alkoxy silane is selected from one or more of silane coupling agent, methyl trimethoxy silane, gamma-glycidoxypropyl trimethoxy silane, vinyl trimethoxy silane, diethyl dimethoxy silane, gamma-aminopropyl triethoxy silane or gamma-mercapto propyl methyl dimethoxy silane;
more preferably, the alkoxy silane is one or more of silane coupling agent, methyl trimethoxy silane or gamma-glycidyl ether oxygen propyl trimethoxy silane;
optionally, the pH is adjusted to 1-6 in S1 using an acid hydrolysis catalyst;
preferably, the acid hydrolysis catalyst is an organic acid and/or an inorganic acid;
more preferably, the acid hydrolysis catalyst is one or more of hydrochloric acid, nitric acid, acetic acid, propionic acid, oxalic acid, maleic acid, benzoic acid, malonic acid, glutaric acid, glycolic acid, and p-toluenesulfonic acid.
3. The method for preparing the antireflection coating liquid according to claim 1, wherein the nanoparticles having a hollow structure are nanosilicon dioxide having a hollow structure and/or nanosilicon dioxide having a hollow structure;
preferably, the nanoparticles with hollow structures are nano-silica with hollow structures;
optionally, the particle size of the hollow structured nanoparticles is 20-100 nm;
more preferably, the particle size of the hollow structured nanoparticles is 40 to 80nm.
4. The method for preparing the anti-reflection coating liquid according to claim 1, wherein the antistatic agent is one or more selected from conductive fillers, cationic antistatic agents, anionic antistatic agents, zwitterionic antistatic agents and nonionic antistatic agents;
optionally, the conductive fillerSelected from carbon black, graphite, nano silver, nano ATO, aluminum-doped zinc oxide AZO, and nano TiO 2 Or MTO;
optionally, the cationic antistatic agent is selected from trialkyl ammonium salts and/or tetraalkyl ammonium salts;
optionally, the anionic antistatic agent is selected from one or more of alkyl phosphate, alkyl benzene sulfonate, alkyl sulfonate or alkyl sulfate;
optionally, the zwitterionic antistatic agent is selected from one or more of alkyl betaine, imidazoline or alkyl dicarboxymethyl ammonium ethyl lactone;
optionally, the nonionic antistatic agent is selected from one or more of polyoxyethylene fatty ether, polyoxyethylene alkyl phenyl ether or glycerin fatty acid ester.
5. The process for preparing an anti-reflective coating liquid according to claim 1, wherein said antifogging agent is selected from the group consisting of a nonionic surfactant, an anionic surfactant or a cationic surfactant;
optionally, the nonionic surfactant is one or more of glycerol ester, polyglycerol ester, sorbitan ester, ethoxylated nonyl phenol, ethoxylated alcohol or carboxylated polyvinyl alcohol;
optionally, the anionic surfactant is an alkyl sulfonate and/or alkyl carboxylate;
optionally, the cationic surfactant is a first order alkali metal cation salt.
6. The method for preparing an anti-reflective coating liquid according to claim 1, wherein the first solvent and the second solvent are independently selected from one or more of alcohols, ethers, esters or ketones;
optionally, the auxiliary agent is selected from one or more of a leveling agent, a defoaming agent or a wetting agent.
7. The method of claim 1 wherein the coating solution is preparedThe preparation method is characterized in that the addition ratio of the alkoxy silane and the water in the S1 is that the hydroxyl in the water and the siloxane SiOR in the alkoxy silane are added 2 The molar ratio of (1-2): 1;
the input mass ratio of the nanoparticles with the hollow structure to the alkoxy silane is (1-5): (1-1.2);
the solid content of the antireflection coating liquid in the S3 is 3-6%, wherein the concentration of the antistatic agent is 0.09-0.80 wt%, the concentration of the antifogging agent is 0.09-0.80 wt%, and the concentration of the auxiliary agent is 0.009-0.09 wt%.
8. The antireflection coating liquid prepared by the method for preparing an antireflection coating liquid according to any one of claims 1 to 7.
9. A dustproof, antifogging and antistatic coating with an antireflection function is characterized by being prepared by preparing the antireflection coating liquid by the preparation method of the antireflection coating liquid according to any one of claims 1 to 7 and/or thermally curing the antireflection coating liquid according to claim 8 at 90-100 ℃;
optionally, the coating has a continuous cross-linked network of porous closed pores;
optionally, the thickness of the coating is 100-150 nm;
optionally, the coating has a light transmittance of 97.12-99.12% and a surface impedance of 10 7 ～10 10 Ω；
Optionally, the coating has an adhesion rating of 5B;
optionally, the coating is in water vapor at 60 ℃ for 30s, and the coating still keeps transparent;
optionally, the coating has a reflectivity of 0.12 to 0.33%.
10. An antistatic optical plastic article characterized in that the dustproof, antifogging, antistatic coating having an antireflection function according to claim 9 is provided on the surface of the optical plastic article.
CN202211107563.1A 2022-09-13 2022-09-13 Coating with antireflection, dustproof, antifogging and antistatic functions and preparation method thereof Pending CN115404003A (en)

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CN103627227A (en) * 2013-11-27 2014-03-12 天津市职业大学 Solar glass self-cleaning antireflection paint and production method thereof
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CN109535780A (en) * 2017-08-15 2019-03-29 中国科学院上海硅酸盐研究所 A kind of super hydrophilic silica coat and preparation method thereof
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CN109704347A (en) * 2019-01-30 2019-05-03 北京科技大学 A kind of hollow silica ball nanocomposite and preparation and application
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CN103627227A (en) * 2013-11-27 2014-03-12 天津市职业大学 Solar glass self-cleaning antireflection paint and production method thereof
CN105439457A (en) * 2015-06-09 2016-03-30 中国南玻集团股份有限公司 Chain or meshed colloidal silica, super hydrophilic self-cleaning anti-reflection coating liquid and preparation application
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