CN113637345B - Water-based environment-friendly wear-resistant organic-inorganic hybrid antifogging coating and preparation thereof - Google Patents
Water-based environment-friendly wear-resistant organic-inorganic hybrid antifogging coating and preparation thereof Download PDFInfo
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Abstract
The invention relates to the field of antifogging coatings, and in particular relates to an aqueous environment-friendly wear-resistant organic-inorganic hybrid antifogging coating. The invention uses aqueous polyurethane-acrylic resin and modified TiO 2 /SiO 2 The hybrid microspheres are used as a main body and compounded with an active diluent, polyacrylamide, a leveling agent and the like; the paint prepared by the method takes water and alcohol as composite solvents, has low content of Volatile Organic Compounds (VOC), and belongs to environment-friendly paint. After the anti-fog coating provided by the invention is cured by UV light, the coating has high hardness and good soaking resistance, has wear resistance and lasting anti-fog performance, and is suitable for the field with anti-fog requirements, such as goggles, swimming goggles, car lamp covers, bathroom mirrors and the like.
Description
Technical Field
The invention relates to the field of antifogging coatings, and in particular relates to an aqueous environment-friendly wear-resistant organic-inorganic hybrid antifogging coating.
Background
Fogging is a common natural phenomenon in daily life because when the temperature reaches or approaches the dew point temperature, water vapor in the air condenses into tiny dew drops to form a fog layer. The atomization phenomenon on the surface of the transparent material can not only cause the light transmittance to be seriously reduced, but also sometimes has serious potential safety hazard, for example, when the agricultural plastic greenhouse or the solar cell panel is condensed, the light transmittance is seriously influenced, so that the solar energy absorption rate is influenced, and the crop yield is reduced or the power generation rate of the solar cell panel is reduced; when the fogging occurs on a medical goggles or a motorcycle helmet, the visual field can be seriously influenced, and a great potential safety hazard exists. In order to prevent the fogging phenomenon, people adopt various anti-fogging measures, and a common heating method is (1) to prevent fogging by keeping the temperature of the surface of the transparent material higher than a dew point through heating, but the method has high cost and strong limitation, and is not suitable for being popularized and used in a large range. (2) The surface of the material is subjected to hydrophilic or hydrophobic treatment, the hydrophobic treatment generally adopts silicon-fluorine-containing high polymer resin, the film forming is difficult, the process is complex, the cost is high, and the atomization phenomenon still occurs when a large amount of water vapor is rapidly condensed on the surface of the material, so that the application in life is less; the hydrophilic treatment can improve the wetting property of the surface of the whole material, and is beneficial to spreading of small water beads on the surface of the material, so that the material has good antifogging property, but the traditional hydrophilic antifogging coating has the following problems: a. generally, volatile solvents such as esters and ethers are adopted, so that the environment pollution is relatively large in the film forming process, and the production cost of the coating and the preparation process cost of the coating are increased; b. the antifogging layer has the problems of poor wear resistance, low hardness, poor soaking resistance and the like.
For example, chinese patent CN105315735 discloses a photo-thermal dual-curing hydrophilic anti-fog coating. The coating is firstly subjected to thermosetting and then photocuring, so that an obtained antifogging layer has good antifogging durability and wear resistance, but the curing process is complex, and meanwhile, the solvent of the coating adopts propylene glycol butyl ether, ethylene glycol butyl ether, propylene glycol methyl ether acetate, alcohol ester-12, propylene glycol phenyl ether, benzyl alcohol and the like, so that the environmental pollution and the resource waste are caused in the film making process; chinese patent CN103980455A discloses a photocuring antifogging coating using polyurethane acrylic resin as matrix resin, and although the antifogging film prepared by the coating has good initial antifogging effect and durable antifogging property, the antifogging film has low hardness and poor wear resistance because of being a pure polymer antifogging film; patent CN1321164C discloses a hydrophilic polymer antifogging coating, the solvent of which is BThe solvent such as glycol monomethyl ether or glycol monoethyl ether has high cost, causes air pollution in the using process, has poor wear resistance and low hardness on the surface of the antifogging film, and limits the using range of the antifogging film. Patent CN111607320A provides a water-based polyurethane-silica sol composite antifogging agent, wherein the main chain segment of the water-based polyurethane is PEG, the problems of weak binding force and insufficient smoothness exist on different base materials in the actual film forming process, and the problems of too high crosslinking degree and hydrophilic performance reduction caused by micropore blockage and no adjustment of surface double bonds are easily caused in the use process of hydrophilic silica microspheres; patent CN201210419958.5 uses nano SiO 2 As core material, TiO 2 Is a shell material, has more complex process in the actual preparation process, and is SiO 2 The actual hydrophilic effect will be greatly reduced after coating.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide the water-based environment-friendly wear-resistant organic-inorganic hybrid antifogging coating, which directly takes water and alcohol as a composite solvent in the preparation process, so that the pollution of solvent volatilization to the environment can be effectively reduced, and the production cost of the coating is reduced.
The purpose of the invention is realized by the following technical scheme:
the invention provides a water-based environment-friendly wear-resistant organic-inorganic hybrid antifogging coating which comprises the following components in parts by weight:
the invention also provides a preparation method of the water-based environment-friendly wear-resistant organic-inorganic hybrid antifogging coating, which comprises the following steps: mixing aqueous polyurethane acrylic resin and TiO 2 /SiO 2 The hybrid microspheres, the reactive diluent, the polyacrylamide, the photoinitiator, the flatting agent, the auxiliary agent, the deionized water, the ethanol or the isopropanol are sequentially added into a container for mixing, the ultrasonic dispersion is carried out in a water bath, and the secondary dispersion is carried out after the solution is clarified.
Specifically, the waterborne polyurethane acrylic resin of the waterborne polyurethane-acrylic resin is prepared by three steps of reactions:
firstly, preparing Polyacrylate (PAA), namely reacting monomers (MMA, AA, St and HEA) and an initiator Azobisisobutyronitrile (AIBN) in different proportions at the temperature of 60-80 ℃ for 8-10 hours, wherein the dosage of the AIBN is 0.5-1.5% of the total mass of the monomers;
step two, preparing a polyurethane resin Prepolymer (PUA), wherein the PUA is prepared from polyether polyol and isophorone diisocyanate, the molar ratio of functional groups of the polyether polyol to the isophorone diisocyanate is (-NCO: -OH is 2: 1), and the molecular weight of polyether polyol is 800-2000;
and thirdly, adding a certain amount of PAA into the PUA, and continuously reacting for 5-6 h at the temperature of 60-80 ℃ to obtain the waterborne polyurethane acrylic resin.
In particular, TiO 2 /SiO 2 The preparation steps of the hybrid microsphere are as follows: (1) TBT/TEOS: H2O: the mass ratio of Et-OH (absolute ethyl alcohol) is 1-2: 3-8: 3-8, wherein the TBT/TEOS molar ratio is 0.98-0.8, the pH value is 2-3.5, the stirring speed is 500-1000 rpm, the reaction temperature is 50-80 ℃, and the reaction time is 3-5 hours; (2) and then adding one or more of KH-570, KH-560, HEA or MTMS, continuously stirring, ending the reaction after 3-5 h, and adjusting the pH value to 6.8-7.2 for normal temperature storage.
Preferably, the pH is adjusted by adding acetic acid, citric acid, acrylic acid, sodium hydroxide or potassium hydroxide.
Preferably, TiO 2 /SiO 2 The grain diameter of the hybrid microspheres is less than 800nm, and the modified TiO 2 /SiO 2 The purpose of the hybrid microspheres is to introduce TiO into the antifogging film for stably fixing the antifogging film 2 /SiO 2 The purpose of the hybrid microspheres is to increase the hardness and the wear resistance of the photocuring antifogging film and increase the adhesion of the antifogging film on the surface of glass.
Preferably, the reactive diluent comprises one or more of acrylic acid, methacrylic acid, hydroxyethyl methacrylate, hydroxyethyl acrylamide, glycidyl methacrylate and pentaerythritol triacrylate, wherein the introduction of the high-functional reactive diluent is beneficial to improving the crosslinking density of the cured film, and can further improve the hardness, wear resistance and soaking resistance of the antifogging film.
Preferably, the molecular weight of the polyacrylamide is 200-800 ten thousand, and the aim of introducing the acrylamide is to improve the antifogging property of the antifogging film and improve the film-forming property of the coating by adjusting the viscosity of the coating.
Preferably, the photoinitiator is at least one of 184D, MBF, TPO, 1173D, and the purpose of compounding the photoinitiators with different wavebands is to further improve the curing efficiency of the antifogging coating, reduce the curing time, and improve the crosslinking density of the cured film.
Preferably, the leveling agent is at least one of BYK-333, BYK-306, BYK-3700, BYK-358N and BYK-3720.
Preferably, the auxiliary agent is a polymerization inhibitor and an antioxidant, and the addition of the auxiliary agent is beneficial to improving the storage stability of the antifogging coating.
Preferably, the solvent of the aqueous environment-friendly wear-resistant organic-inorganic hybrid antifogging coating is a compound solvent of water and ethanol or isopropanol, wherein the ethanol or isopropanol is added to facilitate water volatilization in the pre-drying process.
The invention also provides application of the water-based environment-friendly wear-resistant organic-inorganic hybrid antifogging coating in antifogging, and the water-based environment-friendly wear-resistant organic-inorganic hybrid antifogging coating is sequentially subjected to film coating, pre-drying and UV (ultraviolet) light curing. Wherein the pre-drying temperature is 75-85 ℃, the pre-drying time is 5-15 min, and the curing energy is 40000-6000 mJ/cm 2 。
Compared with the prior art, the invention has the following beneficial effects:
1) MMA and St are introduced into the waterborne polyurethane acrylic resin in the waterborne coating, and the purpose is to enhance the adhesive force of the antifogging coating on the surfaces of PMMA, PS and other substrates.
2) Pure SiO 2 When the microspheres encounter oil and other non-volatile substances, micro-pore blockage is easy to occur to cause the decrease of antifogging performance; pure TiO2 microspheres will lose hydrophilicity in the absence of lightDoes not have antifogging effect, but adopts TiO due to the self-cleaning characteristic 2 /SiO 2 The hybrid microspheres can combine the advantages of the two to reach the most hydrophilic antifogging performance.
3)TiO 2 /SiO 2 The hybrid microsphere is modified by a silane coupling agent without C ═ C double bonds, the silane coupling agent is mainly used for adjusting the functionality of the surface of silica sol, the surface of the modified microsphere has carbon-carbon double bonds, the particle size of the modified microsphere is less than 800nm, and the modified microsphere is uniformly fixed in an antifogging film because the modified microsphere participates in photocuring reaction, so that the antifogging film is endowed with good wear resistance on one hand, and has polarity close to that of glass on the other hand, and the cured film also has good adhesive force on the surface of the glass. The introduction of the high-functionality waterborne polyurethane-acrylic resin and the action of the small-molecule active diluent greatly increase the crosslinking density of the antifogging curing film, so that the integral friction resistance of the surface of the antifogging film is enhanced, the increase of the crosslinking density prevents water molecules from corroding the antifogging film in the soaking process of the antifogging film, and the soaking resistance of the antifogging film is further enhanced.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will aid those skilled in the art in further understanding the present invention, but are not intended to limit the invention in any manner. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the invention.
Example 1
An aqueous environment-friendly wear-resistant organic-inorganic hybrid coating comprises the following raw materials in parts by weight:
the preparation method of the coating comprises the following steps: sequentially adding the raw materials into a 200ml beaker, carrying out ultrasonic treatment in a water bath at 50 ℃ for 15min, continuing to mechanically stir for secondary dispersion after the solution is clear, and transferring the solution into a brown shading bottle for storage after the solution is uniformly dispersed.
In the aspect of coating the antifogging film, 200ul of antifogging raw liquid is dripped on an acrylic plate with the thickness of 5 multiplied by 2mm, a wire rod is adopted for carrying out blade coating uniformly, the acrylic plate is placed in an oven with the temperature of 80 ℃ for pre-drying for 5min after standing for 2min, and then UV light curing is carried out, wherein the curing energy is 40000mJ/cm 2 。
Example 2
An aqueous environment-friendly wear-resistant organic-inorganic hybrid coating comprises the following raw materials in parts by weight:
the preparation method of the coating comprises the following steps: sequentially adding the raw materials into a 200ml beaker, carrying out ultrasonic treatment in a water bath at 50 ℃ for 15min, continuing to mechanically stir for secondary dispersion after the solution is clarified, and transferring the solution into a brown shading bottle for storage after the solution is uniformly dispersed.
In the aspect of coating the antifogging film, 200ul of antifogging raw liquid is dropped on an acrylic plate with the thickness of 5 multiplied by 2mm, a wire bar is adopted for carrying out blade coating uniformly, the obtained product is placed in an oven with the temperature of 80 ℃ for pre-drying for 5min after standing for 2min, and then UV light curing is carried out, wherein the curing energy is 40000mJ/cm 2 。
Example 3
An aqueous environment-friendly wear-resistant organic-inorganic hybrid coating comprises the following raw materials in parts by weight:
the preparation method of the coating comprises the following steps: sequentially adding the raw materials into a 200ml beaker, carrying out ultrasonic treatment in a water bath at 50 ℃ for 15min, continuing to mechanically stir for secondary dispersion after the solution is clear, and transferring the solution into a brown shading bottle for storage after the solution is uniformly dispersed.
In the aspect of coating the antifogging film, 200ul of antifogging raw liquid is dripped on an acrylic plate with the thickness of 5 multiplied by 2mm, a wire rod is adopted for carrying out blade coating uniformly, the acrylic plate is placed in an oven with the temperature of 80 ℃ for pre-drying for 5min after standing for 2min, and then UV light curing is carried out, wherein the curing energy is 40000mJ/cm 2 。
Comparative example 4
An aqueous environment-friendly wear-resistant organic-inorganic hybrid coating comprises the following raw materials in parts by weight:
the preparation method of the coating comprises the following steps: sequentially adding the raw materials into a 200ml beaker, carrying out ultrasonic treatment in a water bath at 50 ℃ for 15min, continuing to mechanically stir for secondary dispersion after the solution is clear, and transferring the solution into a brown shading bottle for storage after the solution is uniformly dispersed.
In the aspect of coating the antifogging film, 200ul of antifogging raw liquid is dropped on an acrylic plate with the thickness of 5 multiplied by 2mm, a wire bar is adopted for carrying out blade coating uniformly, the obtained product is placed in an oven with the temperature of 80 ℃ for pre-drying for 5min after standing for 2min, and then UV light curing is carried out, wherein the curing energy is 40000mJ/cm 2 。
Comparative example 5
An aqueous environment-friendly wear-resistant organic-inorganic hybrid coating comprises the following raw materials in parts by weight:
the preparation method of the coating comprises the following steps: sequentially adding the raw materials into a 200ml beaker, carrying out ultrasonic treatment in a water bath at 50 ℃ for 15min, continuing to mechanically stir for secondary dispersion after the solution is clarified, and transferring the solution into a brown shading bottle for storage after the solution is uniformly dispersed.
In the aspect of coating the antifogging film, 200ul of antifogging raw liquid is dripped on an acrylic plate with the thickness of 5 multiplied by 2mm, a wire rod is adopted for carrying out blade coating uniformly, the acrylic plate is placed in an oven with the temperature of 80 ℃ for pre-drying for 5min after standing for 2min, and then UV light curing is carried out, wherein the curing energy is 40000mJ/cm 2 。
And (4) performance testing:
the film coating performance of examples 1 to 3 was tested, and the initial antifogging property, antifogging property after immersion, water contact angle, hardness, adhesion, and abrasion resistance were tested.
The specific performance test items and corresponding methods are as follows:
firstly, antifogging performance testing:
placing the antifogging sheet above a 65 ℃ water bath kettle at a distance of 5cm from the liquid level, fumigating for 30s, and taking a picture to observe the antifogging performance of the antifogging sheet.
Antifogging performance criteria: a level, uniform water film; b level, wherein the area of less than 50% of the B level is provided with uneven water films; c level, wherein more than 50% of the area has uneven water films; grade D, condensation is formed in an area smaller than 50%; class E, condensation is formed in an area larger than 50%; and class F, wherein fog is formed in the area less than 50%, and class G, wherein fog is formed in the area more than 50%.
Secondly, testing the water contact angle:
2.5uL of ultrapure water was dropped on the surface of the cured film, and the contact angle was measured at room temperature by using a contact angle measuring instrument.
Thirdly, testing hardness:
refer to national standard GB/T6739 Pencil determination method for hardness of paint film
Fourthly, testing adhesive force:
testing the adhesive force of the sample by using a 3M adhesive tape by adopting a white lattice method;
the evaluation method comprises the following steps:
level 0-smooth edge of the line, no paint film falls off at the edge and the intersection of the line;
level 1-there is a small piece of paint film falling off at the cross point of the scribe line, but the falling area is less than 5%;
2, small paint films fall off at the edge and the intersection of the scribing line, but the falling area is between 5 and 15 percent;
grade 3, wherein a film is formed on the edge and the intersection of the scribing line and falls off, but the falling area is 15-35%;
4, a film is formed on the edge and the intersection of the scribing line and is peeled off, but the peeling area is 35-65%;
grade 5-there is a film patch falling off at the edge and intersection of the scribe line, but the area of the fall off is greater than 65%.
Fifth, wear resistance test
The number of surface scratches was recorded using 0000# steel wool, 200g weight, 200 rubs.
And (3) testing results:
| anti-fog device | Water contact angle | Hardness of | Adhesion force | Wear-resistant | |
| Example 1 | Class A | 6.996° | 2H | Level 0 | 5 strips |
| Example 2 | Class A | 10.213° | 3H | Grade 0 | 0 strip |
| Example 3 | Class A | 10.194° | 3H | Grade 0 | 0 strip |
| Comparative example 4 | Class D | 30.415° | B | Grade 5 | 50 strips |
| Comparative example 5 | Class D | 35.173° | B | Grade 0 | 80 strips |
Claims (7)
1. A preparation method of an aqueous environment-friendly wear-resistant organic-inorganic hybrid antifogging coating is characterized by comprising the following steps: the water-based environment-friendly wear-resistant organic-inorganic hybrid antifogging coating comprises the following components in parts by weight:
30-50 parts of waterborne polyurethane acrylic resin;
TiO 2 /SiO 2 15-25 parts of hybrid microspheres;
20-30 parts of a reactive diluent;
2-5 parts of polyacrylamide;
3-5 parts of a photoinitiator;
0.5-1 part of a leveling agent;
0.5-1 part of an auxiliary agent;
80-100 parts of deionized water;
20-40 parts of ethanol or isopropanol;
the auxiliary agent is a polymerization inhibitor and an antioxidant;
the preparation method comprises the following steps: mixing aqueous polyurethane acrylic resin and TiO 2 /SiO 2 Sequentially adding hybrid microspheres, reactive diluent, polyacrylamide, photoinitiator, flatting agent, auxiliary agent, deionized water, ethanol or isopropanol into a container for mixing, ultrasonically dispersing in water bath, and performing secondary dispersion by mechanically stirring after the solution is clarified;
the TiO is 2 /SiO 2 The preparation steps of the hybrid microsphere are as follows:
（1）TiO 2 /SiO 2 preparing hybrid microspheres: tetrabutyl titanate (TBT)/tetraethyl orthosilicate (TEOS): h 2 O: the mass ratio of the absolute ethyl alcohol is 1-2: 3-8: 3-8, wherein the TBT/TEOS molar ratio is 0.98-0.8, the pH value is 2-3.5, the stirring speed is 500-1000 rpm, the reaction temperature is 50-80 ℃, and the reaction time is 3-5 hours;
(2) and then adding a silane coupling agent KH-570, continuously stirring, finishing the reaction after 3-5 h, and adjusting the pH value to 6.8-7.2 for normal-temperature storage.
2. The preparation method of the aqueous environment-friendly wear-resistant organic-inorganic hybrid antifogging coating according to claim 1, characterized in that the aqueous polyurethane acrylic resin is prepared by three steps of reactions:
first step, preparation of Polyacrylate (PAA): methyl Methacrylate (MMA), Acrylic Acid (AA), styrene (St) and hydroxyethyl acrylate (HEA) in different proportions are used as monomers, and Azobisisobutyronitrile (AIBN) is used as an initiator, and the mixture is reacted for 8-10 hours at the temperature of 60-80 ℃, wherein the dosage of the Azobisisobutyronitrile (AIBN) is 0.5% -1.5% of the total mass of the monomers;
step two, preparing a polyurethane resin prepolymer: the polyether polyol is prepared from polyether polyol and isophorone diisocyanate, wherein the molar ratio of functional groups of the polyether polyol to the isophorone diisocyanate is-NCO: -OH is 2: 1, the molecular weight of polyether polyol is 800-2000;
step three, preparing the waterborne polyurethane acrylic resin: adding a certain amount of Polyacrylate (PAA) into the polyurethane resin prepolymer, and continuously reacting for 5-6 h at the temperature of 60-80 ℃.
3. The preparation method of the aqueous environment-friendly wear-resistant organic-inorganic hybrid antifogging coating of claim 1, wherein the reactive diluent comprises one or more of acrylic acid, methacrylic acid, hydroxyethyl methacrylate, hydroxyethyl acrylamide, glycidyl methacrylate, pentaerythritol triacrylate.
4. The preparation method of the water-based environment-friendly wear-resistant organic-inorganic hybrid antifogging coating according to claim 1, wherein the molecular weight of the polyacrylamide is 200-800 ten thousand.
5. The preparation method of the aqueous environment-friendly wear-resistant organic-inorganic hybrid antifogging coating according to claim 1, characterized in that the photoinitiator is at least one of 184D, MBF, TPO, 1173D.
6. The preparation method of the water-based environment-friendly wear-resistant organic-inorganic hybrid antifogging coating as claimed in claim 1, wherein the leveling agent is at least one of BYK-333, BYK-306, BYK-3700, BYK-358N and BYK-3720.
7. The application of the water-based environment-friendly wear-resistant organic-inorganic hybrid antifogging coating prepared by the preparation method according to any one of claims 1 to 6 in antifogging is characterized in that the water-based environment-friendly wear-resistant organic-inorganic hybrid antifogging coating is subjected to film coating, pre-baking and UV (ultraviolet) light curing in sequence.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104817949B (en) * | 2015-05-18 | 2017-03-08 | 湖南松井新材料有限公司 | Ultraviolet light curing anti fogging coating |
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| CN109666119B (en) * | 2018-12-25 | 2020-07-24 | 湖南松井新材料股份有限公司 | Water-based antifogging resin, water-based antifogging coating composition and preparation method thereof |
| CN109652001A (en) * | 2018-12-25 | 2019-04-19 | 广州聚达光电有限公司 | A kind of UV solidification glue of high transparency, low haze |
| CN110256951A (en) * | 2019-05-24 | 2019-09-20 | 深圳市嘉卓成科技发展有限公司 | A kind of aqueous UV curing coating and preparation method thereof and application method |
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