CN113372807B - Continuous friction-resistant ultraviolet-curing antifogging coating composition and preparation of coating thereof - Google Patents
Continuous friction-resistant ultraviolet-curing antifogging coating composition and preparation of coating thereof Download PDFInfo
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Abstract
The invention aims to provide an ultraviolet curing antifogging coating composition with continuous friction resistance and a preparation method thereof. The super-hydrophilic coating obtained after photocuring of the coating has excellent continuous antifogging performance and excellent abrasion resistance, so that some defects of antifogging coatings on the market are overcome, the coating still has excellent antifogging performance after being soaked in water for a long time (such as swimming goggles), the continuous antifogging time can reach 1-2 years, and the coating is very suitable for being applied to the fields with antifogging requirements, such as swimming goggles, car lamps, windshields, bathroom mirrors, optical lens materials and the like.
Description
Technical Field
The invention belongs to the field of photocureable coating, and particularly relates to an ultraviolet-cured antifogging coating composition.
Background
When the temperature of the water vapor in the air is lower than the dew point, the water vapor is condensed into tiny liquid drops to form mist. Such adverse effects often occur on windows, bathroom mirrors, glasses, swimming and diving glasses, windshields, optics lenses, car lights, indicator lights, agricultural films, and the like, which are transparent materials closely related to our lives. As a result of the atomization of water droplets on the surface of the transparent material, not only is the light transmittance decreased to affect the vision, but also a hazard is sometimes generated, for example, when the droplets condense on the lens surface of a precision analysis instrument such as an infrared optical microscope, the accuracy of the analysis thereof is lowered.
To solve these problems, the surface of the material is usually treated to be hydrophobic or hydrophilic. The hydrophobic treatment method is not common, on one hand, the hydrophobic material has higher price and poor wear resistance, and on the other hand, the antifogging effect is difficult to achieve. The organic hydrophilic coating is low in price, and the water immersion resistance and the wear resistance of the organic hydrophilic coating can be improved through modification. Compared with a hydrophobic coating treatment method, the organic hydrophilic coating is convenient to construct and low in cost.
At present, the research of super-hydrophilicity is mainly focused at home and abroad, for example, groups capable of forming hydrogen bonds such as carboxyl, amino, sulfydryl and hydroxyl or some ionic groups are introduced into the surface of the coating: when the groups or ions are introduced, the surface of the coating reaches a super-hydrophilic state, water vapor is highly spread on the surface of the base material after being condensed to form a uniform water film, and the diffuse reflection of tiny water drops to light is eliminated to achieve the aim of preventing fog. The current way for preparing the super-hydrophilicity is mainly through physical blending, chemical surface modification and chemical bonding. The continuous antifogging performance and the wear resistance of the antifogging coating on the current market cannot be balanced, and the antifogging performance is obviously reduced after the coating is used for a period of time. In addition, water molecules of the coatings can continuously permeate in the water to damage the coatings, and continuous antifogging is difficult to realize, so that the water immersion resistance and the wear resistance are two major problems to be solved urgently by the antifogging coatings.
The domestic patent CN102795791A discloses a wear-resistant super-hydrophilic anti-reflection coating, which is prepared by repeatedly depositing poly-diallyl dimethyl ammonium chloride and sodium polystyrene sulfonate to prepare a double-layer structure with 5-20 layers, and then repeatedly depositing poly-diallyl dimethyl ammonium chloride and SiO with the grain diameter of 10-40 nm 2 Preparing a double-layer structure with 3-8 layers by using the suspension of the spherical nano particles, and then carrying out hydrothermal treatment at 100-140 ℃ and quenching in a muffle furnace at 600-800 ℃ for 100-300 s to obtain the required coating. Although the coating prepared by the method can reach high hardness of 5H and has small water contact angle, the method has the advantages of complex steps, general lasting antifogging property and large energy consumption, and is only suitable for users with special and high requirements on performance. The domestic patent CN102086348A discloses a preparation method of a polyurethane curing acrylate resin antifogging coating, and the coating is composed of hydrophilic acrylic resin, a closed polyether isocyanate curing agent and a catalyst dibutyltin dilaurate. The coating has hardness more than 2H and good wear resistance, but has general continuous antifogging property, long time is needed in the curing process, segmented curing (50-120 ℃) is needed, and the process is complex.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide an ultraviolet curing antifogging coating composition with continuous friction resistance and a preparation method thereof. The super-hydrophilic coating obtained after photocuring of the coating has excellent continuous antifogging performance and excellent abrasion resistance, so that some defects of antifogging coatings on the market are overcome, the coating still has excellent antifogging performance after being soaked in water for a long time (such as swimming goggles), the continuous antifogging time can reach 1-2 years, and the coating is very suitable for being applied to the fields with antifogging requirements, such as swimming goggles, car lamps, windshields, bathroom mirrors, optical lens materials and the like.
The purpose of the invention is realized by the following technical scheme:
the invention provides an ultraviolet curing antifogging coating composition, which comprises the following components:
3-5 parts of a surfactant;
photocurable acrylic hydrophilic resin (20-38 parts);
photocurable acrylic hydrophobic resin (20-25 parts);
a photocurable inorganic component (10-15 parts);
zwitterionic polymer resin (5-10 parts);
photocurable hydrophobic small molecules (10-15 parts);
photo-curable hydrophilic small molecules (5-10 parts);
leveling agent (1-2 parts);
3-5 parts of an initiator;
the composition also comprises a solvent, and the weight of the solvent is 0.3-3 times of the total weight of other components.
The surfactant is one or more of nonylphenol polyoxyethylene ether, octylphenol polyoxyethylene ether and polyvinyl alcohol.
The surfactant is an antifogging component in the composition and can enhance the antifogging performance of the coating.
The photo-curable acrylic hydrophilic resin is self-made acrylate (single function) with a side chain containing unsaturated double bonds, the main framework of the photo-curable acrylic hydrophilic resin is polyurethane acrylate, and the photo-curable acrylic hydrophilic resin is an oligomer formed by polymerizing hydrophilic fatty alcohol-polyoxyethylene ether (AEO), diisocyanate and acrylate.
The structure and preparation process reaction formula of the photocurable acrylic hydrophilic resin are as follows:
wherein R is 1 ,R 2 ,R 3 All are alkyl chain segments consisting of 1-18 carbon atoms.
The specific preparation method of the light-curable acrylic hydrophilic resin comprises the following steps: mixing the diisocyanate and the acrylate, wherein the solvent is ethyl acetate. Reacting at 40-60 ℃ for 1-2 hours, adding fatty alcohol-polyoxyethylene ether (AEO) and continuing to react for 3-4 hours to obtain the product. The feeding molar ratio of diisocyanate, acrylate and fatty alcohol-polyoxyethylene ether (AEO) is about 1-1.3:2-2.4:2-2.2.
The fatty alcohol polyoxyethylene ether (AEO) is one or more of lauryl alcohol polyoxyethylene ether, cetyl alcohol polyoxyethylene ether and stearyl alcohol polyoxyethylene ether.
Preferably, the molecular weight of the fatty alcohol-polyoxyethylene ether (AEO) is between 500 and 2000
The diisocyanate is one or more of isophorone diisocyanate (IPDI), dicyclohexyl methane diisocyanate (HMDI) and Hexamethylene Diisocyanate (HDI).
The acrylate comprises one or more of hydroxyethyl methacrylate (HEMA), hydroxyethyl acrylate (HEA), pentaerythritol triacrylate (PETA).
The purpose of adding the fatty alcohol-polyoxyethylene ether after the reaction of the acrylic ester is to introduce more double bonds into the prepared light-curable acrylic hydrophilic resin.
The photo-curable hydrophilic resin is an antifogging component in the composition, can enhance the antifogging performance of the coating, and can improve the mechanical performance and the continuous antifogging performance of the coating after Ultraviolet (UV) curing.
The photocurable acrylic hydrophobic resin is epoxy acrylic resin with the functionality higher than or equal to 4.
The photo-curable acrylic hydrophobic resin is obtained by polymerizing epoxy resin and acrylic ester as monomers.
The epoxy resin is a bifunctional epoxy resin and comprises one or more of bisphenol A epoxy resin and glycidyl ether epoxy resin.
The acrylate is one or more of pentaerythritol triacrylate (PETA), pentaerythritol diacrylate (PEDA).
The specific preparation method of the photocurable acrylic hydrophobic resin comprises the following steps: mixing the epoxy resin and the acrylic ester, adding triethylamine as a catalyst, and taking ethyl acetate as a solvent. Reacting at 80-120 deg.c for 5-8 hr. The molar ratio of the epoxy resin to the acrylate fed is about 1:2.2-1:2.5.
the photo-curable acrylic hydrophobic resin can improve the mechanical property of the coating after being cured by ultraviolet and has good adhesive force on the base material.
The photo-curable inorganic component comprises hollow transparent SiO with carbon-carbon double bond 2 And/or TiO 2 And (3) nanoparticles.
The hollow transparent SiO 2 And/or TiO 2 The preparation method of the nano-particles comprises two steps:
the first step is to synthesize hollow transparent SiO 2 And/or TiO 2 And (3) nanoparticles. The specific method comprises the following steps: adding TEOS or tetrabutyl titanate and methanol into a reaction container, slowly dropwise adding oxalic acid solution as a catalyst, and stirring at normal temperature for 30min. Adding ammonia water and polyacrylic acid into another beaker, adding into a reaction vessel at equal time of 5 times, adding 1 time every 1h, wherein the total reaction time is about 6h, and centrifugally washing the obtained product with absolute ethyl alcohol for 2 times to obtain hollow transparent SiO 2 And TiO 2 And (3) sol. The solvent is evaporated to dryness to obtain hollow transparent SiO 2 /TiO 2 And (3) nanoparticles.
The second step is hollow transparent SiO containing double bonds 2 /TiO 2 And (3) nanoparticles. The specific method is to mix the hollow transparent SiO 2 /TiO 2 Dispersing the nano particles in ethanol, adding a silane coupling agent KH570, stirring at room temperature for 4-6h, and centrifugally washing with absolute ethanol for 2 times.
Hollow transparent SiO 2 /TiO 2 The nanoparticles are prepared by coating SiO with 2 /TiO 2 Coating salt in sol and then removing the salt to obtain the SiO 2 /TiO 2 The nano particles are hollow particles, so that the scattering of light is reduced and the effect of transparency is achieved.
The invention improves the strength of the coating by hybridizing the light-curable inorganic component and the light-curable organic component.
The amphoteric ion polymer resin is a kind of polymer resin which is electrically neutral as a whole and contains both anion and cation groups on the same monomer side chain. The amphoteric ion polymer resin has good hydrophilic performance, is an antifogging component in the composition and can enhance the antifogging performance of the coating.
The cationic group type of the zwitterionic polymer resin is quaternary ammonium salt cation, and the anionic group types mainly comprise 3 types: sulfonate anions, carboxylate anions and phosphate anions. The zwitterionic polymer resin thus includes betaine Sulfonate (SB), betaine Carboxylate (CB), and Phosphorylcholine (PC) with a poly (meth) acrylate backbone.
According to the invention, the organic light-curable acrylic hydrophilic resin, the organic light-curable acrylic hydrophobic resin and the zwitterionic polymer resin form a cross-linked interpenetrating network, so that the hardness and the mechanical strength of the coating are improved, the surfactant can be locked, and the anti-fog durable time is prolonged.
The light-curable hydrophobic small molecule comprises one or more of 1, 6-hexanediol diacrylate (HDDA), pentaerythritol tetraacrylate (PETA 4) and dipentaerythritol hexaacrylate (DPHA).
The photocurable hydrophobic micromolecules can be crosslinked with photocurable hydrophilic and hydrophobic resin when the coating is photocured, so that the adhesive force of the coating on a base material is improved.
The photo-curable hydrophilic-containing small molecule comprises one or more of acrylic acid, itaconic acid and hydroxyethyl acrylate.
The photo-curable hydrophilic micromolecules can be crosslinked with photo-curable hydrophilic and hydrophobic resin during photo-curing of the coating, so that the anti-fog capability of the coating is improved.
The leveling agent is a substance which can effectively reduce the surface tension of the coating, improve the leveling property and uniformity of the coating, and promote the coating to form a flat, smooth and uniform coating film in the drying film-forming process.
The leveling agent is an acrylate leveling agent, and the molecular weight is 6000-20000.
The photoinitiator is a compound which can absorb energy with certain wavelength in an ultraviolet region (250-420 nm) to generate free radicals, cations and the like so as to initiate the polymerization, crosslinking and curing of monomers.
The photoinitiator includes one or more of 2-hydroxy-2-methyl-1-phenyl acetone (1173), 1-hydroxycyclohexyl phenyl ketone (184), 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (TPO).
The solvent is one or more of ethyl acetate, butyl acetate, isopropanol and ethanol.
The invention determines the appropriate ratio of the components of the formulation by a number of experimental attempts. If the photo-curable acrylic hydrophilic resin is too high, the hydrophilic photo-curable micromolecules are too high, and the photo-curable acrylic hydrophobic resin is too low,
the film obtained after the final photocuring has good hydrophilicity, which can cause the final film to have poor water resistance and poor continuous antifogging property; too low of the photo-curable acrylic hydrophilic resin, too low of the hydrophilic photo-curable small molecule and too high of the photo-curable acrylic hydrophobic resin can result in too poor hydrophilicity of the final coating film, larger initial water contact angle and no antifogging property.
If the amount of the photoinitiator is more than 5 parts, a large amount of free radicals can be generated under ultraviolet irradiation, so that the molecular weight of a final three-dimensional network polymer formed after the obtained coating is cured is low, the coating is brittle, the adhesive force is poor, and the coating cost is increased; if the amount of the photoinitiator is less than 1 part, radicals may be insufficiently generated under ultraviolet irradiation, resulting in a large amount of residual non-photopolymerizable resin and monomer, resulting in poor surface dryness and stickiness of the final coating film, which cannot be used at all.
When the amount of the solvent is more than 3 times the total weight of the other components, the coating is too thin and the thickness of the coating film is too low, resulting in too low hardness and poor abrasion resistance of the final coating film. If the amount of the solvent is less than 0.3 times of the total weight of the other components, the viscosity of the coating is too high, which tends to cause poor leveling of the coating film and too thick thickness of the coating film, and may also cause incomplete curing.
The preparation method of the ultraviolet curing antifogging coating comprises the following steps: accurately weighing each component, and mixing a surfactant, a light-curable acrylic hydrophilic resin, a light-curable acrylic hydrophobic resin, a light-curable inorganic component, a zwitterionic polymer resin, a light-curable hydrophobic micromolecule and a light-curable hydrophilic micromolecule; adding solvent, mixing and stirring for 0.5-1h, adding photoinitiator and flatting agent, and mixing for 0.5h to obtain the final product.
The preparation method of the ultraviolet curing antifogging coating comprises the following steps: coating the ultraviolet curing antifogging composition stock solution on a plate, pre-baking for 2-3min at 60-80 ℃, curing for 30-60s by ultraviolet LED light, and controlling the energy to be 500-1000mJ/cm 2 The coating mode is one of spray coating, curtain coating, drop coating, blade coating or roll coating.
The invention also provides an article comprising a sheet and an antifogging coating on the surface of the sheet, wherein the antifogging coating is obtained by curing the continuous friction-resistant uv-curable antifogging coating composition of any of the above.
The plate material selected by the coating is one of glass, a PC (polycarbonate) plate, a PMMA (polymethyl methacrylate) plate and PET (polyethylene terephthalate).
The ultraviolet curing antifogging composition stock solution can be coated on living goods such as bathroom mirrors (glass), swimming goggles (PC), car lampshades (PMMA) and the like in a manner consistent with that of plates.
The ultraviolet curing antifogging coating prepared by the invention is used for detecting the antifogging performance of the coating through a water contact angle test and a water bath fumigation test. Water bath fumigation is a common anti-fogging performance test method, the temperature difference between water vapor and a base material exists in a water bath, and the untreated base material is easy to fog.
The water resistance test method comprises the following steps: and placing the base material coated with the ultraviolet curing antifogging coating in water to soak for 72h-90h, and then carrying out an antifogging test, wherein the antifogging performance is not attenuated.
The wear resistance of the ultraviolet curing antifogging coating is tested by a wear resistance tester.
The ultraviolet light curing antifogging coating is subjected to a high-temperature accelerated aging test, a test sample is placed in an oven at the temperature of 200 ℃ for 1000-1500 hours, and the coating does not obviously fall off, peel off or wrinkle before and after the test aging.
The ultraviolet curing antifogging coating is subjected to a salt corrosion resistance test, and is soaked in a 5% sodium chloride solution for 500-1000 hours, so that the coating does not obviously fall off, peel off or wrinkle before and after aging.
According to the ultraviolet curing antifogging coating disinfection water immersion resistance test, a sample is immersed in disinfection water for 200-500 hours, and the coating does not obviously fall off, peel off or wrinkle before and after aging.
The ultraviolet curing antifogging coating is subjected to environmental test, a sample is placed in an open air environment for 1-2 years, and the coating does not obviously fall off, peel off or wrinkle before and after aging.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention adopts the light-curable hydrophilic resin with excellent hydrophilicity, and is matched with the light-curable hydrophobic resin, the light-curable hydrophobic micromolecules and the light-curable hydrophilic micromolecules of the high officer, and the light-curable hydrophilic micromolecules form a network structure with cross-linked hydrophilic and hydrophobic parts after light curing. Wherein the hydrophilic part has excellent hydrophilic property so that water drops are easily spread on the coating to form a water film without fogging. The hydrophobic part plays a role of an anchoring point in the coating, the crosslinking density is increased, the coating is ensured not to be dissolved due to swelling when meeting a large amount of water, and not only can the continuous antifogging performance be ensured, but also the wear resistance can be improved.
2. The strength of the coating is improved by hybridization of the light-curable inorganic component and the light-curable organic component.
3. The organic light-curable acrylic hydrophilic resin, the organic light-curable acrylic hydrophobic resin and the zwitterionic polymer resin form a cross-linked interpenetrating network, so that the hardness and the mechanical strength of the coating are improved, the surfactant can be locked, and the antifogging durability is prolonged.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. 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 present invention.
Example 1
Preparation of Photocurable acrylic hydrophilic resin A
0.1mol of isophorone diisocyanate (IPDI) and 0.2mol of hydroxyethyl acrylate (HEA) are mixed, and the solvent is ethyl acetate. After reacting for 2 hours at 40 ℃, 0.2mol of lauryl polyoxyethylene ether is added to continue to react for 3 hours to obtain the catalyst.
Example 2
Preparation of Photocurable acrylic hydrophilic resin B
1.3mol dicyclohexylmethane diisocyanate (HMDI) and 2.4mol hydroxyethyl methacrylate (HEMA) were mixed in ethyl acetate as solvent. Reacting at 50 ℃ for 1 hour, adding 2.2mol of cetyl alcohol polyoxyethylene ether, and continuing to react for 4 hours to obtain the product.
Example 3
Preparation of Photocurable acrylic hydrophilic resin C
1mol of Hexamethylene Diisocyanate (HDI) and 2.4mol of pentaerythritol triacrylate (PETA) in ethyl acetate as solvent. Reacting for 2 hours at 60 ℃, adding 2.2mol of octadecanol polyoxyethylene ether, and continuing to react for 4 hours to obtain the product.
Example 4
Preparation of Photocurable acrylic hydrophobic resin a
1mol of bisphenol A epoxy resin and 2.2mol of pentaerythritol triacrylate (PETA) are mixed, 0.01mol of triethylamine is additionally added as a catalyst, and the solvent is ethyl acetate. After 5 hours of reaction at 80 ℃.
Example 5
Preparation of Photocurable acrylic hydrophobic resin b
1mol of glycidyl ether epoxy resin and 2.5mol of pentaerythritol diacrylate (PEDA) are mixed, 0.02mol of triethylamine is additionally added as a catalyst, and the solvent is ethyl acetate. After reaction for 8 hours at 120 ℃.
Example 6
Double bond-containing hollow transparent SiO 2 Preparation of nanoparticles
Adding 1mol TEOS and 30ml methanol into a reaction container, slowly dropwise adding 0.1mol oxalic acid solution as a catalyst, and stirring for 30min at normal temperature. Adding 3.5ml of ammonia water and 3.8ml of polyacrylic acid into another beaker, adding the mixture into a reaction vessel for 5 times in equal parts, adding the mixture for 1 time every 1h, reacting the mixture for 30min at room temperature after the mixture is completely added, and centrifugally washing the obtained product for 2 times by using absolute ethyl alcohol to obtain hollow transparent SiO 2 And (3) sol. The solvent is evaporated to dryness to obtain hollow transparent SiO 2 And (3) nanoparticles.
The obtained 0.1mol of hollow transparent SiO 2 Dispersing the nano particles in ethanol, adding 0.3mol of silane coupling agent KH570, stirring at room temperature for 4h, and centrifugally washing with absolute ethanol for 2 times to obtain the nano particles.
Example 7
Double bond-containing hollow transparent TiO 2 Preparation of nanoparticles
1.2mol of tetraethyl titanate and 30ml of methanol are added into a reaction vessel, 0.15mol of oxalic acid solution is slowly dropped as a catalyst, and the mixture is stirred for 30min at normal temperature. Adding 3.5ml of ammonia water and 3.8ml of polyacrylic acid into another beaker, adding the mixture into a reaction vessel for 5 times in equal parts, adding the mixture for 1 time every 1 hour, reacting the mixture for 30min at room temperature after completely adding the mixture, and centrifugally washing the obtained product for 2 times by using absolute ethyl alcohol to obtain hollow transparent TiO 2 And (3) sol. Evaporating the solvent to dryness to obtain hollow transparent TiO 2 And (3) nanoparticles.
The obtained 0.15mol of hollow transparent TiO 2 Dispersing the nano particles in ethanol, adding 0.3mol of silane coupling agent KH570, stirring at room temperature for 4h, and centrifugally washing with absolute ethanol for 2 times to obtain the nano particles.
Example 8
Preparation of ultraviolet light curing antifogging coating composition
The preparation method of the ultraviolet curing antifogging coating composition comprises the following steps: accurately weighing each component, and mixing a surfactant, a light-curable acrylic hydrophilic resin, a light-curable acrylic hydrophobic resin, a light-curable inorganic component, a zwitterionic polymer resin, a light-curable hydrophobic micromolecule and a light-curable hydrophilic micromolecule; adding solvent, mixing and stirring for 0.5-1h, adding photoinitiator and flatting agent, and mixing for 0.5h to obtain the final product.
The components and contents of the ultraviolet light curing antifogging coating composition are shown in table 1, in the present invention, the solvent may be one or more of ethyl acetate, butyl acetate, isopropanol, and ethanol, in this embodiment, butyl acetate is used: isopropyl alcohol: ethanol =4:3: 3 (volume ratio) as solvent, wherein the total weight of the solvent is 0.3-3 times of the total weight of other components.
Table 1: ultraviolet curing antifog coating composition component and content
Example 9
Preparation of ultraviolet light curing antifogging coating on plate
Coating stock solutions of ultraviolet curing antifogging composition formulas #1 to #6 obtained in example 8 on a plate, pre-drying for 2-3min at 60-80 ℃, and curing by ultraviolet LED light for 30-60s at 500-1000mJ/cm energy 2 The coating mode is one of spray coating, curtain coating, drop coating, blade coating or roll coating. The sheet material in the present invention may be one of glass, PC (polycarbonate) sheet, PMMA (polymethyl methacrylate) sheet, PET (polyethylene terephthalate).
Example 10
Preparation of ultraviolet light curing antifogging coating on product
The uv-curable anti-fog composition formulations #1 to #6 obtained in example 8 were applied to living goods such as bathroom mirror (glass), swimming goggles (PC), car light cover (PMMA), etc. in the same manner as in example 9.
Example 11
Performance testing of the antifog coatings of examples 9-10
The water contact angle tester is used for testing the water contact angle: the water contact angle is between 8 and 18 degrees.
The antifogging performance of the coating is detected by a water bath fumigation test: heating water in a water bath to 65-70 ℃, putting the sample coated with the anti-fog coating above the water bath for fumigating for 10s at a position 10cm above the water bath, wherein the fogging phenomenon does not occur to all samples.
And (3) testing the water resistance: and (3) placing the sample coated with the ultraviolet curing antifogging coating in water, soaking for 72-90 h, and then carrying out a water bath fumigation antifogging test, wherein the antifogging performance is not attenuated.
The abrasion resistance testing machine tests the abrasion resistance: the weight is 200g, the testing tool is wool felt, the coating does not obviously fall off, peel off or wrinkle after being circularly wiped for 10000 times, and the antifogging property is not attenuated.
High-temperature accelerated aging test: and (3) placing the test sample into a 200 ℃ oven, and testing for 1000-1500 hours, wherein the coating does not obviously fall off, peel off or wrinkle before and after the test aging.
And (3) testing salt corrosion resistance: 5 percent sodium chloride solution is soaked for 500 to 1000 hours, and the coating does not obviously drop, peel off or wrinkle before and after aging.
And (3) disinfectant fluid soaking resistance test: the sample is soaked in the disinfectant for 200-500 hours, and the coating does not obviously fall off, peel off or wrinkle before and after aging.
And (3) environmental testing: the sample is placed in an open air environment for 1-2 years, and the coating does not obviously fall off, peel off or wrinkle before and after aging.
Claims (9)
1. The continuous friction-resistant ultraviolet curing antifogging coating composition comprises the following components in parts by weight:
3-5 parts of a surfactant;
20-38 parts of photo-curable acrylic hydrophilic resin;
20-25 parts of photocurable acrylic hydrophobic resin;
10-15 parts of a photocurable inorganic component;
5-10 parts of zwitterionic polymer resin;
10-15 parts of light-curable hydrophobic micromolecules;
5-10 parts of photo-curable hydrophilic micromolecules;
1-2 parts of a leveling agent;
1-5 parts of an initiator;
the composition also comprises a solvent, and the weight of the solvent is 0.3-3 times of the total weight of other components;
the photo-curable inorganic component comprises hollow transparent SiO with carbon-carbon double bond 2 And/or TiO 2 A nanoparticle;
the hollow transparent SiO 2 And/or TiO 2 The preparation method of the nano-particles comprises two steps:
the first step is to synthesize hollow transparent SiO 2 And/or TiO 2 Adding TEOS and/or tetrabutyl titanate and methanol into a reaction container, slowly dropwise adding oxalic acid solution as a catalyst, stirring at normal temperature, adding ammonia water and polyacrylic acid, reacting to obtain a product, and centrifugally washing with absolute ethyl alcohol to obtain hollow transparent SiO 2 And/or TiO 2 Dissolving in water, evaporating solvent to obtain hollow transparent SiO 2 And/or TiO 2 A nanoparticle;
the second step is to synthesize hollow transparent SiO containing double bonds 2 And/or TiO 2 Nanoparticles prepared by mixing the hollow transparent SiO 2 And/or TiO 2 Dispersing the nano particles in ethanol, adding a silane coupling agent KH570, stirring at room temperature, and centrifugally washing with absolute ethanol.
2. The uv-curable anti-fog coating composition for continuous abrasion resistance according to claim 1, characterized in that: the surfactant is one or more of nonylphenol polyoxyethylene ether, octylphenol polyoxyethylene ether or polyvinyl alcohol.
3. The continuous friction-resistant UV-curable anti-fog coating composition of claim 1, wherein: the photocurable acrylic hydrophilic resin is self-made acrylate with a side chain containing unsaturated double bonds, the main framework of the photocurable acrylic hydrophilic resin is polyurethane acrylate, and the photocurable acrylic hydrophilic resin is an oligomer polymerized by using hydrophilic fatty alcohol-polyoxyethylene ether (AEO), diisocyanate and acrylate as monomers.
4. The UV-curable anti-fog coating composition of claim 3, wherein: the specific preparation method of the photocurable acrylic hydrophilic resin comprises the following steps: mixing diisocyanate and acrylate, wherein the solvent is ethyl acetate; reacting at 40-60 ℃ for 1-2 hours, adding fatty alcohol-polyoxyethylene ether (AEO) and continuing to react for 3-4 hours to obtain the product; the feeding molar ratio of diisocyanate to acrylate to fatty alcohol-polyoxyethylene ether (AEO) is 1-1.3:2-2.4:2-2.2.
5. The continuous friction-resistant UV-curable anti-fog coating composition of claim 1, wherein: the photocurable acrylic hydrophobic resin is epoxy acrylic resin with the functionality higher than or equal to 4; the photocurable acrylic hydrophobic resin is obtained by polymerizing epoxy resin and acrylic ester as monomers.
6. The UV-curable anti-fog coating composition for continuous abrasion resistance according to claim 5, wherein: the specific preparation method of the photocurable acrylic hydrophobic resin comprises the following steps: mixing the epoxy resin and the acrylate, adding triethylamine as a catalyst, and taking ethyl acetate as a solvent; reacting at 80-120 deg.c for 5-8 hr to obtain the product; the feeding molar ratio of the epoxy resin to the acrylate is 1:2.2-1:2.5.
7. a method for preparing the continuous friction-resistant UV-curable antifogging coating composition according to any one of claims 1 to 6, characterized in that: accurately weighing the following components, surfactant, light-curable acrylic hydrophilic resin, light-curable acrylic hydrophobic resin, light-curable inorganic component, zwitterionic polymer resin, light-curable hydrophobic micromolecule and light-curable hydrophilic micromolecule; adding solvent, mixing and stirring for 0.5-1h, adding photoinitiator and flatting agent, and mixing to obtain the final product.
8. An antifogging coating is prepared by coating the continuous friction-resistant ultraviolet-curing antifogging coating composition of any one of claims 1 to 6 on glass, a PC (polycarbonate) plate, a PMMA (polymethyl methacrylate) plate or PET (polyethylene terephthalate) plate in a spraying, curtain coating, drop coating, blade coating or roll coating manner, pre-baking at the temperature of 60-80 ℃ for 2-3min, curing by ultraviolet LED (light-emitting diode) light for 30-60s and controlling the energy to be 500-1000mJ/cm 2 。
9. An article comprising a sheet and an antifog coating on said sheet, wherein said antifog coating is obtained by curing the continuous friction-resistant uv-curable antifog coating composition of any one of claims 1 to 6.
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| CN115260893B (en) * | 2022-08-30 | 2023-06-09 | 广东邦固化学科技有限公司 | Self-repairing UV (ultraviolet) photo-curing anti-fog resin polymer and preparation method thereof |
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