CN114231160A - Antifogging coating and preparation method and application thereof - Google Patents
Antifogging coating and preparation method and application thereof Download PDFInfo
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- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
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Abstract
The invention provides an antifogging coating and a preparation method and application thereof, wherein the antifogging coating comprises the combination of urethane acrylate, a photoinitiator and a fluorine-containing temperature-sensitive nano material; the fluorine-containing temperature-sensitive nano material comprises a two-dimensional nano material and an N-isopropyl acrylamide-based polymer layer coated on the two-dimensional nano material; the N-isopropyl acrylamide-based polymer layer is connected with a fluorine-containing group. The coating formed after the anti-fog coating is cured has super-hydrophilicity and excellent anti-fog performance; meanwhile, the coating has temperature sensitivity, the polarity and the oleophobicity of the coating can be amplified at the environmental temperature higher than 32 ℃, and the coating has good antifouling performance and self-cleaning performance. Moreover, the antifogging coating is a photocuring system, has stable coating property and good water resistance and reliability, and can fully meet the long-term application requirements of the antifogging coating in medical instruments such as endoscopes and laparoscopes.
Description
Technical Field
The invention belongs to the technical field of polymer coatings, and particularly relates to an antifogging coating and a preparation method and application thereof.
Background
Under the condition of certain humidity and temperature difference, water vapor is easy to condense on the surface of a transparent material (such as glass, polycarbonate, acrylic and the like) to form a layer of fog, so that the transparency or the reflectivity of the transparent material is poor, and the visibility of an observation field is influenced. In the medical field, the fogging phenomenon of the lens after the endoscope head, the laparoscope head and the like enter the body of a patient brings great inconvenience to diagnosis and treatment. Therefore, it is one of the research directions of endoscopes and laparoscopes to prevent lens fogging.
Compared with technologies such as heating antifogging, washing antifogging and wiping antifogging, the method for improving the lens material to enable the lens material to have antifogging performance is convenient. The conventional material improvement technology is to form an antifogging coating on the surface of the lens, so as to slow down or prevent the fogging or dewing phenomenon on the surface of the substrate. The antifogging coating can be divided into the following types according to the types of active ingredients: inorganic antifogging coating, organic-inorganic hybridization antifogging coating. The antifogging mechanism of the antifogging coating is mainly divided into two types: one is to use a hydrophilic material, reduce the contact angle of water on the surface of the material, spread and thin the water, reduce diffuse reflection, and enable light rays to better penetrate through the material; the other method is to use a hydrophobic material to increase the contact angle of water on the surface of the material, and small water drops formed by water vapor are difficult to stay on the surface due to the action of gravity after being gathered into larger water drops, thereby achieving the anti-fog purpose.
CN109734325A discloses a preparation method of super-hydrophobic antifogging glass, which comprises the following steps: uniformly coating the super-hydrophobic antifogging coating on a glass sheet, and drying at 60-70 ℃ for 1-2h to obtain super-hydrophobic antifogging glass; the preparation method of the super-hydrophobic antifogging coating comprises the following steps: firstly, preparing hydrophobic nano-silica dispersion liquid, then adding heptadecafluorodecyltrimethoxysilane and gamma-aminopropyltriethoxysilane into the dispersion liquid, and hydrolyzing to obtain hydrophobic nano-silica sol; and mixing the epoxy resin emulsion with a modified polyamide epoxy curing agent to obtain the epoxy resin emulsion. However, the hydrophobic coating has poor antifogging effect in endoscope and laparoscope because the lens of the medical instrument is very small, the water drops formed by the generated fog are also very small, and the surface acting force of the very small water drops and the coating is larger than the self gravity, so that the antifogging effect cannot be effectively realized.
Hydrophilic materials have significant performance and practical advantages in antifogging medical device lenses, for example, CN111849333A discloses a SiO2The preparation method of the hydrophilic modified UV-cured waterborne polyurethane antifogging coating comprises the following steps: firstly, synthesizing waterborne polyurethane, then preparing nano silica sol by hydrolyzing tetraethoxysilane TEOS, and finally, preparing nano silica sol by hydrolyzing tetraethoxysilane TEOSIntroducing the sol into aqueous polyurethane to generate a cross-linking structure in situ, and curing to obtain SiO2Hydrophilic modified UV-cured waterborne polyurethane antifogging coating. The SiO prepared by the method2The hydrophilic modified UV-cured waterborne polyurethane antifogging coating has good hydrophilicity, but the water resistance and the corrosion resistance are poor, so that the hydrophilic modified UV-cured waterborne polyurethane antifogging coating is not suitable for long-term use. CN109971007A discloses a normal temperature curing polyurethane antifogging film, which is obtained by curing a polyurethane prepolymer and a curing cross-linking agent; the polyurethane prepolymer is mainly prepared by polymerizing isocyanate or isocyanate polymer, polyoxyethylene ether, dimethylol fatty acid and hydroxyl-containing surfactant; the curing crosslinking agent is trifunctional aziridine. The antifogging film has better light transmittance and antifogging performance, but the antifogging effective time is short, and the antifogging effect can be gradually attenuated after the film is placed for a period of time; the reason is that the polyurethane antifogging film is cured at normal temperature, and the inevitable reaction is continuously generated at the room temperature, so that the surfactant cannot be enriched on the surface for a long time, and the antifogging performance is reduced or even completely loses efficacy.
Therefore, the current antifogging coating still has defects in antifogging effectiveness, stability and resistance (such as water resistance, corrosion resistance, aging resistance and the like); meanwhile, medical instruments have high requirements on cleanliness and cleanness of lenses, and the existing antifogging coating cannot meet multiple performance requirements. Therefore, the development of a coating material having stable performance and having both antifogging property and antifouling property is an important research point in the field.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide an antifogging coating and a preparation method and application thereof, wherein the antifogging coating is prepared by compounding urethane acrylate, a photoinitiator and a fluorine-containing temperature-sensitive nano material, and the coating has super-hydrophilic surface property and excellent antifogging performance; meanwhile, a coating formed by the antifogging coating has temperature sensitivity, micro-morphology transformation occurs in an environment higher than 32 ℃, and the oleophobic property of the coating is amplified, so that the antifogging coating has low adhesion and good antifouling property.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides an antifog coating comprising a combination of urethane acrylate, a photoinitiator, and a fluorine-containing thermo-sensitive nanomaterial; the fluorine-containing temperature-sensitive nano material comprises a two-dimensional nano material and an N-isopropyl acrylamide-based polymer layer coated on the two-dimensional nano material; the N-isopropyl acrylamide-based polymer layer is connected with a fluorine-containing group.
The antifogging coating provided by the invention is a photocuring system, and a coating formed by curing is stable in property and has good water resistance, aging resistance and corrosion resistance; the fluorine-containing temperature-sensitive nano material contains an N-isopropyl acrylamide based polymer layer and a fluorine-containing group, has hydrophilicity, a strong polar group and good temperature sensitivity, is compounded with urethane acrylate and a photoinitiator, so that a coating after the coating is cured has strong interaction with water molecules, and water is quickly spread on the surface of the coating to be in a super-hydrophilic state, thereby having an excellent anti-fog effect; meanwhile, due to the existence of the N-isopropyl acrylamide based polymer layer, the coating can generate micro-morphology and functional group transformation under the condition of being higher than 32 ℃ (the phase transition temperature of poly N-isopropyl acrylamide), so that the rearrangement of fluorine-containing groups on the surface of the coating is promoted, the polarity and the oleophobicity of the coating are amplified, the adhesion of the surface of the coating is reduced, and the antifouling performance is good.
Preferably, the two-dimensional nanomaterial comprises any one of graphene, nano-zirconium phosphate or layered clay silicate material or a combination of at least two thereof, and further preferably nano-zirconium phosphate.
Preferably, the layered clay silicate material comprises talc and/or montmorillonite.
Preferably, the particle size of the two-dimensional nanomaterial is 30-3000nm, for example, 50nm, 80nm, 100nm, 300nm, 500nm, 700nm, 900nm, 1000nm, 1200nm, 1500nm, 1800nm, 2000nm, 2200nm, 2500nm or 2800nm, and the specific values therebetween are limited by space and for the sake of brevity, and the invention is not exhaustive and the specific values included in the range are further preferably 100-1500 nm.
Preferably, the polymerized monomers of the N-isopropylacrylamide-based polymer layer include a combination of N-isopropylacrylamide and a hydroxyl-containing acrylate.
Preferably, the molar ratio of the N-isopropylacrylamide to the hydroxyl-containing acrylate is (1.5-5):1, and may be, for example, 1.6:1, 1.8:1, 2:1, 2.2:1, 2.5:1, 2.8:1, 3:1, 3.2:1, 3.5:1, 3.8:1, 4:1, 4.2:1, 4.5:1, or 4.8: 1.
As a preferred technical scheme of the invention, the polymerized monomer comprises the combination of N-isopropyl acrylamide and hydroxyl-containing acrylate, the molar ratio of the N-isopropyl acrylamide to the hydroxyl-containing acrylate is (1.5-5):1, the formed coating has good hydrophilicity and temperature sensitivity, and the hydroxyl-containing acrylate provides a hydroxyl functional group which can be used as a reaction site for introducing a fluorine-containing group. If the content of the N-isopropylacrylamide is too low, the temperature sensitivity of the antifogging coating is not obvious, so that the oleophobic property and the antifouling property of the coating are influenced; if the content of the hydroxyl-containing acrylate is too low, the grafting of fluorine-containing groups is influenced, so that the coating formed by the antifogging coating has fewer polar groups, the oleophobicity is reduced, and the antifouling performance is lower.
Preferably, the hydroxyl-containing acrylate comprises any one of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, or a combination of at least two thereof.
Preferably, the fluorine-containing group is linked to the N-isopropylacrylamide-based polymer layer through a urethane bond.
Preferably, the fluorine-containing group is obtained by reacting fluorine-containing isocyanate with an N-isopropyl acrylamide-based polymer layer (containing hydroxyl), and the fluorine-containing group with strong polarity is anchored on the surface of the temperature-sensitive nano material; meanwhile, when the external temperature changes, the N-isopropyl acrylamide-based polymer layer on the temperature-sensitive nano material is subjected to phase transition, and fluorine-containing groups are extruded and subjected to micro adjustment, so that the surface polarity of a coating formed by the anti-fog coating is enhanced, and the coating has oleophobic property and good antifouling property.
Preferably, the fluorine-containing temperature-sensitive nanomaterial is prepared by a method comprising the following steps:
(1) treating the two-dimensional nano material by using a silane coupling agent containing alkenyl to obtain an alkenyl modified two-dimensional nano material;
(2) mixing the alkenyl modified two-dimensional nanomaterial obtained in the step (1), a polymerization monomer, a cross-linking agent and an initiator, and then reacting to obtain a two-dimensional nanomaterial coated with an N-isopropyl acrylamide based polymer layer;
(3) and (3) reacting the two-dimensional nano material obtained in the step (2) with fluorine-containing isocyanate to obtain the fluorine-containing temperature-sensitive nano material.
Preferably, the alkenyl-containing silane coupling agent includes any one of a vinyl silane coupling agent, a methacrylate silane coupling agent, an allyl silane coupling agent, or an acryloxy silane coupling agent, or a combination of at least two thereof.
Preferably, the mass ratio of the two-dimensional nanomaterial to the alkenyl-containing silane coupling agent in step (1) is (5-100):1, and may be, for example, 8:1, 10:1, 15:1, 20:1, 25:1, 30:1, 35:1, 40:1, 45:1, 50:1, 55:1, 60:1, 65:1, 70:1, 75:1, 80:1, 85:1, 90:1, or 95: 1.
Preferably, the time of the treatment in step (1) is 0.5-10h, for example, 1h, 1.5h, 2h, 2.5h, 3h, 3.5h, 4h, 4.5h, 5h, 6h, 7h, 8h, 9h or 9.5h, and the specific values therebetween are not exhaustive for the invention and for the sake of brevity.
Preferably, the method of processing of step (1) comprises: dispersing a two-dimensional nano material in water, adding an alkenyl-containing silane coupling agent, and treating for 0.5-10h under the stirring condition to obtain the alkenyl modified two-dimensional nano material.
Preferably, the mass ratio of the alkenyl modified two-dimensional nanomaterial to the polymerized monomer is 1 (1-10), and may be, for example, 1:1.5, 1:1:2, 1:2.5, 1:3, 1:3.5, 1:4, 1:4.5, 1:5, 1:5.5, 1:6, 1:6.5, 1:7, 1:7.5, 1:8, 1:8.5, or 1:9, 1:9.5, etc.
Preferably, the crosslinking agent comprises N, N' -methylenebisacrylamide.
Preferably, the mass ratio of the crosslinking agent to the polymerizable monomer is (0.005-0.2):1, and may be, for example, 0.006:1, 0.008:1, 0.01:1, 0.03:1, 0.05:1, 0.07:1, 0.09:1, 0.1:1, 0.11:1, 0.13:1, 0.15:1, 0.17:1, 0.19:1, or the like.
Preferably, the initiator comprises a persulfate initiator.
Preferably, the persulfate initiator comprises any one or a combination of at least two of ammonium persulfate, potassium persulfate, or sodium persulfate.
Preferably, the reaction of step (2) is carried out in the presence of a solvent.
Preferably, the solvent comprises water.
Preferably, the reaction temperature in step (2) is 50-90 ℃, for example, 52 ℃, 55 ℃, 58 ℃, 60 ℃, 62 ℃, 65 ℃, 68 ℃, 70 ℃, 72 ℃, 75 ℃, 78 ℃, 80 ℃, 82 ℃, 85 ℃ or 88 ℃, and the specific values therebetween are limited by space and for the sake of brevity, and the invention is not exhaustive listing the specific values included in the range.
Preferably, the reaction time in step (2) is 1 to 12 hours, for example, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours or 11 hours, and the specific values therebetween are not exhaustive, and the invention is not limited to the specific values included in the ranges for brevity and conciseness.
Preferably, the fluorine-containing isocyanate is obtained by reacting a fluorine-containing monohydric alcohol with a diisocyanate.
Preferably, the fluorine-containing monohydric alcohol comprises any one of trifluoroethanol, hexafluoroisopropanol, heptafluorobutanol, octafluoropentanol, nonafluorooctanol, tridecafluorooctanol or pentadecafluorooctanol, or a combination of at least two of the foregoing.
Preferably, the diisocyanate comprises any one of isophorone diisocyanate, hexamethylene diisocyanate or dicyclohexylmethane diisocyanate or a combination of at least two thereof.
Preferably, the fluorine-containing isocyanate is prepared by a method comprising: and mixing the fluorine-containing monohydric alcohol and diisocyanate and then reacting to obtain the fluorine-containing isocyanate.
The molar ratio of the fluorine-containing monohydric alcohol to the diisocyanate is preferably 1 (1-2), and may be, for example, 1:1.1, 1:1.2, 1:1.3, 1:1.4, 1:1.5, 1:1.6, 1:1.7, 1:1.8, or 1: 1.9.
Preferably, the reaction is carried out in the presence of a solvent.
Preferably, the solvent comprises any one of ethyl acetate, butyl acetate or dioxane or a combination of at least two thereof.
Preferably, the reaction is carried out in the presence of an organotin catalyst.
Preferably, the reaction temperature is 20-50 ℃, for example, 22 ℃, 25 ℃, 28 ℃, 30 ℃, 32 ℃, 35 ℃, 38 ℃, 40 ℃, 42 ℃, 45 ℃ or 48 ℃, and the specific values therebetween are limited by space and for the sake of brevity, and the invention is not exhaustive of the specific values included in the ranges.
Preferably, the mass ratio of the two-dimensional nanomaterial in step (3) to the fluorine-containing isocyanate is 1 (0.1-0.7), and may be, for example, 1:0.15, 1:0.2, 1:0.25, 1:0.3, 1:0.35, 1:0.4, 1:0.45, 1:0.5, 1:0.55, 1:0.6, or 1: 0.65.
As a preferred technical scheme of the invention, the mass ratio of the two-dimensional nanomaterial in the step (3) to the fluorine-containing isocyanate is 1 (0.1-1), so that a proper amount of strong polar fluorine-containing groups are anchored on the surface of the obtained fluorine-containing temperature-sensitive nanomaterial, and a coating formed by an antifogging coating containing the material after curing has hydrophilicity and excellent antifogging effect, is subjected to mass transition under the stimulation of external temperature, amplifies the oleophobic property of the surface and presents good antifouling effect; if the dosage of the fluorine-containing isocyanate is too small, the fluorine-containing group of the fluorine-containing temperature-sensitive nano material is less, and the oleophobic property and antifouling property of the coating surface are poor; if the amount of the fluorine-containing isocyanate is too large, the surface energy of the coating is low, water does not well wet and spread, and the hydrophilicity and antifogging effect are reduced.
Preferably, the reaction of step (3) is carried out in the presence of an organotin catalyst.
Preferably, the mass of the organotin catalyst is 0.01 to 0.3%, for example 0.03%, 0.05%, 0.07%, 0.09%, 0.1%, 0.12%, 0.15%, 0.18%, 0.2%, 0.22%, 0.25%, or 0.28%, based on 100% by mass of the fluorine-containing isocyanate, and specific values therebetween, not to be limiting to space and for the sake of brevity, the invention is not exhaustive of the specific values encompassed by the scope.
Preferably, the reaction of step (3) is carried out in the presence of a solvent.
Preferably, the solvent comprises any one of ethyl acetate, butyl acetate or dioxane or a combination of at least two thereof.
Preferably, the reaction temperature in step (3) is 20-50 ℃, for example, 22 ℃, 25 ℃, 28 ℃, 30 ℃, 32 ℃, 35 ℃, 38 ℃, 40 ℃, 42 ℃, 45 ℃ or 48 ℃, and the specific values therebetween are not exhaustive, and the invention is not limited to the specific values included in the range for brevity and conciseness.
Preferably, the reaction time of step (3) is 0.5-6h, for example, 1h, 1.5h, 2h, 2.5h, 3h, 3.5h, 4h, 4.5h, 5h or 5.5h, and the specific values therebetween are not exhaustive, and for brevity and clarity, the invention is not intended to be exhaustive.
Preferably, the antifogging coating comprises the following components in parts by weight:
40-60 parts of urethane acrylate
0.5-10 parts of photoinitiator
8-20 parts of fluorine-containing temperature-sensitive nano material.
The urethane acrylate is 40-60 parts by weight, such as 41 parts, 43 parts, 45 parts, 47 parts, 49 parts, 50 parts, 51 parts, 53 parts, 55 parts, 57 parts or 59 parts by weight, and specific values therebetween are not exhaustive, and the invention is not limited to specific values included in the ranges for brevity and conciseness.
The photoinitiator is present in an amount of 0.5 to 10 parts by weight, for example 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts or 9 parts, and the specific values therebetween are not exhaustive for the purpose of brevity and clarity.
The fluorine-containing temperature-sensitive nanomaterial is 8-20 parts by weight, for example, 9 parts, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, 16 parts, 17 parts, 18 parts or 19 parts by weight, and specific values therebetween are not exhaustive, and for brevity and clarity, the specific values included in the range are not limited to the space.
In the invention, the dosage of the polyurethane acrylate and the photoinitiator is calculated based on the effective components (solid content) of the polyurethane acrylate and the photoinitiator, and the polyurethane acrylate and the photoinitiator do not contain solvents, diluents, dispersing agents, auxiliary agents and the like.
Preferably, the photoinitiator comprises any one of or a combination of at least two of a benzil photoinitiator, an aromatic ketone photoinitiator, an acylphosphorus oxide photoinitiator or a benzoin photoinitiator.
Preferably, the photoinitiator comprises any one of 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl acetone, 2-methyl-2- (4-morpholinyl) -1- (4- (methylthio) phenyl) -1-propanone, benzoin dimethyl ether, benzoin ethyl ether, benzoin isopropyl ether, phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide, 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide or ethyl 2,4, 6-trimethylbenzoyl phenyl phosphonate, or a combination of at least two thereof.
Preferably, the anti-fog coating further comprises a diluent.
Preferably, the diluent comprises any one of water, propylene glycol methyl ether, propylene glycol ethyl ether, ethylene glycol butyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monopropyl ether, or dipropylene glycol monobutyl ether, or a combination of at least two thereof.
Preferably, the amount of the diluent in the antifogging coating is 1 to 20 parts, for example, 3 parts, 5 parts, 7 parts, 9 parts, 10 parts, 11 parts, 13 parts, 15 parts, 17 parts or 19 parts, and specific points between the above points, which are limited by space and for the sake of brevity, are not exhaustive and are included in the scope of the present invention.
Preferably, the antifogging coating comprises the following components in parts by weight:
in a second aspect, the present invention provides a method for preparing the anti-fog coating according to the first aspect, the method comprising: and mixing and uniformly dispersing the urethane acrylate, the photoinitiator and the fluorine-containing temperature-sensitive nano material to obtain the antifogging coating.
Preferably, the mixed material further comprises a diluent.
Preferably, the preparation method comprises: mixing the polyurethane acrylate with a diluent, and then mixing and uniformly dispersing the polyurethane acrylate with the fluorine-containing temperature-sensitive nano material; and adding a photoinitiator into the mixture, and uniformly mixing to obtain the antifogging coating.
In a third aspect, the present invention provides a use of the anti-fog coating of the first aspect in a medical device.
Preferably, the medical instrument comprises an endoscope or a laparoscope.
Preferably, the antifogging coating is used as follows: and coating the antifogging coating on the surface of a substrate, standing, and curing by ultraviolet irradiation to obtain the coating.
Compared with the prior art, the invention has the following beneficial effects:
in the antifogging coating provided by the invention, a specific fluorine-containing temperature-sensitive nano material is compounded with the polyurethane acrylate and the photoinitiator, so that a coating formed by the antifogging coating after curing has stronger interaction with water molecules, the coating has super-hydrophilicity, the water contact angle is less than 28 degrees and can be as low as below 10 degrees, and the antifogging performance reaches level 1; meanwhile, the coating has good temperature sensitivity, the environmental temperature higher than 32 ℃ can promote the property transformation of the coating, the polarity and the oleophobicity of the coating are enlarged, the oil contact angle is larger than 110 degrees, the adhesion of oily substances on the surface is reduced, the antifouling property and the self-cleaning property are good, and the antifouling property reaches level 1. Moreover, the antifogging coating is a photocuring system formed by compounding specific components, has stable coating property and good water resistance and reliability, and can fully meet the long-term application requirements of the antifogging coating in medical instruments such as endoscopes and laparoscopes.
Drawings
FIG. 1 is a graph of the coating contact angle test results for the anti-fog coating provided in example 1;
FIG. 2 is a graph of the coating contact angle test results for the anti-fog coating provided in example 7;
FIG. 3 is a graph of the coating contact angle test results for the anti-fog coating provided in example 8;
FIG. 4 is a graph of the coating contact angle test results for the anti-fog coating provided in example 9;
FIG. 5 is a graph of the coating contact angle test results for the anti-fog coating provided in example 10;
FIG. 6 is a graph of the coating contact angle test results for the antifog coating provided in comparative example 1;
FIG. 7 is a graph of the coating contact angle test results for the antifog coating provided in comparative example 2;
FIG. 8 is a graph of the coating contact angle test results for the antifog coating provided in comparative example 3;
FIG. 9 is a graph of the coating antifogging performance test results of the antifogging coatings provided in examples 1, 7-9;
fig. 10 is a graph showing the results of the antifogging water resistance test of the coatings of the antifogging coatings provided in examples 1, 8 and 10.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Preparation example 1
A fluorine-containing temperature-sensitive nano material comprises nano zirconium phosphate and an N-isopropyl acrylamide base polymer layer coated on the nano zirconium phosphate, wherein a fluorine-containing group is grafted on the N-isopropyl acrylamide base polymer layer, and the preparation method comprises the following steps:
(1) dispersing nano zirconium phosphate in water to form a suspension; adding vinyl triethoxysilane with the mass ratio of nano zirconium phosphate to vinyl triethoxysilane being 10:1, processing for 6h under stirring, centrifugally separating, washing and drying to obtain alkenyl modified nano zirconium phosphate;
(2) dispersing 1 part of the alkenyl modified nano zirconium phosphate obtained in the step (1) in deionized water, exhausting air in a reaction bottle, adding 6 parts of a polymerization monomer (the molar ratio of N-isopropylacrylamide to hydroxyethyl methacrylate is 4:1) and 0.4 part of N, N' -methylene Bisacrylamide (BIS) into the reaction bottle under the protection of nitrogen, stirring for 40min, uniformly dispersing, adding 0.22 part of Ammonium Persulfate (APS), heating to 70 ℃, reacting for 8h, centrifuging the reaction dispersion, and drying to obtain the nano zirconium phosphate coated with the N-isopropylacrylamide-based polymer layer;
(3) dispersing the nano zirconium phosphate obtained in the step (2) in ethyl acetate, and adding fluorine-containing isocyanate and dibutyltin dilaurate into the ethyl acetate, wherein the mass ratio of the nano zirconium phosphate to the fluorine-containing isocyanate is 1:0.3, and the mass of the dibutyltin dilaurate is 0.1% of that of the fluorine-containing isocyanate; controlling the temperature to be 30 ℃, stirring and reacting for 5 hours, then centrifugally separating, washing and drying to obtain the fluorine-containing temperature-sensitive nano material; wherein the fluorine-containing isocyanate is obtained by reacting hexafluoroisopropanol with isophorone diisocyanate in a molar ratio of 1: 1.5.
Preparation example 2
A fluorine-containing temperature-sensitive nano material comprises nano zirconium phosphate and an N-isopropyl acrylamide base polymer layer coated on the nano zirconium phosphate, wherein a fluorine-containing group is grafted on the N-isopropyl acrylamide base polymer layer, and the preparation method comprises the following steps:
(1) dispersing nano zirconium phosphate in water to form a suspension; adding gamma-methacryloxypropyltrimethoxysilane into the mixture, wherein the mass ratio of the nano-zirconium phosphate to the gamma-methacryloxypropyltrimethoxysilane is 50:1, treating for 6 hours under the stirring condition, performing centrifugal separation, washing and drying to obtain alkenyl modified nano-zirconium phosphate;
(2) dispersing 1 part of the alkenyl modified nano zirconium phosphate obtained in the step (1) in deionized water, exhausting air in a reaction bottle, adding 9 parts of a polymerization monomer (the molar ratio of N-isopropylacrylamide to hydroxyethyl methacrylate is 2:1) and 0.5 part of BIS into the reaction bottle under the protection of nitrogen, stirring for 60min, uniformly dispersing, adding 0.3 part of APS, heating to 70 ℃, reacting for 8h, centrifuging and drying the reaction dispersion liquid to obtain the nano zirconium phosphate coated with the N-isopropylacrylamide-based polymer layer;
(3) dispersing the nano zirconium phosphate obtained in the step (2) in ethyl acetate, and adding fluorine-containing isocyanate and dibutyltin dilaurate into the ethyl acetate, wherein the mass ratio of the nano zirconium phosphate to the fluorine-containing isocyanate is 1:0.6, and the mass of the dibutyltin dilaurate is 0.1% of that of the fluorine-containing isocyanate; controlling the temperature to be 30 ℃, stirring and reacting for 6 hours, then centrifugally separating, washing and drying to obtain the fluorine-containing temperature-sensitive nano material; wherein, the fluorine-containing isocyanate is obtained by reacting hexafluoroisopropanol with hexamethylene diisocyanate in a molar ratio of 1: 1.5.
Preparation example 3
A fluorine-containing temperature-sensitive nano material comprises nano zirconium phosphate and an N-isopropyl acrylamide base polymer layer coated on the nano zirconium phosphate, wherein a fluorine-containing group is grafted on the N-isopropyl acrylamide base polymer layer, and the preparation method comprises the following steps:
(1) dispersing nano zirconium phosphate in water to form a suspension; adding vinyl trimethoxy silane into the mixture, wherein the mass ratio of the nano zirconium phosphate to the vinyl trimethoxy silane is 20:1, treating the mixture for 6 hours under the stirring condition, performing centrifugal separation, washing and drying to obtain alkenyl modified nano zirconium phosphate;
(2) dispersing 1 part of the alkenyl modified nano zirconium phosphate obtained in the step (1) in deionized water, exhausting air in a reaction bottle, adding 5 parts of a polymerization monomer (the molar ratio of N-isopropylacrylamide to hydroxyethyl acrylate is 5:1) and 0.2 part of BIS into the reaction bottle under the protection of nitrogen, stirring for 30min, uniformly dispersing, adding 0.1 part of APS, heating to 70 ℃, reacting for 8h, centrifuging and drying the reaction dispersion liquid to obtain the nano zirconium phosphate coated with the N-isopropylacrylamide-based polymer layer;
(3) dispersing the nano zirconium phosphate obtained in the step (2) in ethyl acetate, and adding fluorine-containing isocyanate and dibutyltin dilaurate into the ethyl acetate, wherein the mass ratio of the nano zirconium phosphate to the fluorine-containing isocyanate is 1:0.2, and the mass of the dibutyltin dilaurate is 0.1% of that of the fluorine-containing isocyanate; controlling the temperature to be 30 ℃, stirring and reacting for 6 hours, then centrifugally separating, washing and drying to obtain the fluorine-containing temperature-sensitive nano material; wherein the fluorine-containing isocyanate is obtained by reacting heptafluorobutanol with hexamethylene diisocyanate in a molar ratio of 1: 1.5.
Preparation example 4
A fluorine-containing temperature-sensitive nano material comprises nano zirconium phosphate and an N-isopropyl acrylamide base polymer layer coated on the nano zirconium phosphate, wherein a fluorine-containing group is grafted on the N-isopropyl acrylamide base polymer layer, and the preparation method comprises the following steps:
(1) dispersing nano zirconium phosphate in water to form a suspension; adding vinyl triethoxysilane with the mass ratio of the nano zirconium phosphate to the vinyl triethoxysilane being 30:1, processing for 6h under stirring, centrifugally separating, washing and drying to obtain alkenyl modified nano zirconium phosphate;
(2) dispersing 1 part of the alkenyl modified nano zirconium phosphate obtained in the step (1) in deionized water, exhausting air in a reaction bottle, adding 8 parts of a polymerization monomer (the molar ratio of N-isopropylacrylamide to hydroxyethyl methacrylate is 4:1) and 0.5 part of BIS into the reaction bottle under the protection of nitrogen, stirring for 60min, uniformly dispersing, adding 0.25 part of APS, heating to 70 ℃, reacting for 8h, centrifuging and drying the reaction dispersion liquid, and obtaining the nano zirconium phosphate coated with the N-isopropylacrylamide-based polymer layer;
(3) dispersing the nano zirconium phosphate obtained in the step (2) in ethyl acetate, and adding fluorine-containing isocyanate and dibutyltin dilaurate into the ethyl acetate, wherein the mass ratio of the nano zirconium phosphate to the fluorine-containing isocyanate is 1:0.4, and the mass of the dibutyltin dilaurate is 0.1% of that of the fluorine-containing isocyanate; controlling the temperature to be 30 ℃, stirring and reacting for 8 hours, then centrifugally separating, washing and drying to obtain the fluorine-containing temperature-sensitive nano material; wherein, the fluorine-containing isocyanate is obtained by reacting hexafluoroisopropanol with hexamethylene diisocyanate in a molar ratio of 1: 1.5.
Preparation example 5
A fluorine-containing temperature-sensitive nano material comprises nano zirconium phosphate and an N-isopropyl acrylamide-based polymer layer coated on the nano zirconium phosphate, wherein the N-isopropyl acrylamide-based polymer layer is grafted with a fluorine-containing group, and the fluorine-containing temperature-sensitive nano material is only different from the preparation example 4 in that the mass ratio of the nano zirconium phosphate to fluorine-containing isocyanate in the step (3) is 1: 0.8; other raw materials, amounts and preparation methods were the same as those of preparation example 4.
Preparation example 6
A fluorine-containing temperature-sensitive nano material comprises nano zirconium phosphate and an N-isopropyl acrylamide-based polymer layer coated on the nano zirconium phosphate, wherein the N-isopropyl acrylamide-based polymer layer is grafted with a fluorine-containing group, and the fluorine-containing temperature-sensitive nano material is only different from the preparation example 4 in that the mass ratio of the nano zirconium phosphate to fluorine-containing isocyanate in the step (3) is 1: 0.05; other raw materials, amounts and preparation methods were the same as those of preparation example 4.
Comparative preparation example 1
A fluorine-containing nanomaterial comprising zirconium nanophosphate and a polymer layer coated thereon, the polymer layer having a fluorine-containing group grafted thereon, which differs from preparation example 4 only in that N-isopropylacrylamide in step (2) is replaced with an equimolar amount of acrylamide; other raw materials, amounts and preparation methods were the same as those of preparation example 4.
The following examples and comparative examples according to the invention relate to materials comprising:
(1) urethane acrylate: the water-based polyurethane acrylate emulsion has the solid content of 43 percent, the solvent is water, the water-based polyurethane acrylate emulsion is purchased from Yangxing chemical, and the weight parts in the examples and the comparative examples are calculated by the solid content;
(2) photoinitiator (2): 2-hydroxy-2-methyl-1-phenylpropanone;
(3) fluorine-containing temperature-sensitive nano material: preparation examples 1 to 6;
(4) diluent agent: propylene glycol methyl ether.
Example 1
An antifogging coating comprises the following components in parts by weight:
the preparation method of the antifogging coating comprises the following steps: mixing the urethane acrylate and the diluent according to the formula amount, adding the fluorine-containing temperature-sensitive nano material, and mixing and uniformly dispersing; and adding a photoinitiator into the system, and uniformly mixing to obtain the antifogging coating.
Example 2
An antifogging coating comprises the following components in parts by weight:
the preparation method of the antifogging coating is the same as that of the example 1.
Example 3
An antifogging coating comprises the following components in parts by weight:
the preparation method of the antifogging coating is the same as that of the example 1.
Examples 4 to 8
An antifogging coating is only different from the antifogging coating in example 1 in that fluorine-containing temperature-sensitive nano materials are respectively fluorine-containing temperature-sensitive nano materials provided in preparation examples 2 to 6; other raw materials, components and preparation methods are the same as those of example 1.
Example 9
An antifogging coating which is different from the antifogging coating in the embodiment 1 only in that the fluorine-containing temperature-sensitive nano material accounts for 5 parts by weight; other raw materials, components and preparation methods are the same as those of example 1.
Example 10
An antifogging coating which is different from the antifogging coating in the embodiment 1 only in that the weight part of the fluorine-containing temperature-sensitive nano material is 26 parts; other raw materials, components and preparation methods are the same as those of example 1.
Comparative example 1
An antifogging coating comprises the following components in parts by weight:
the nano material is the nano zirconium phosphate coated with the N-isopropyl acrylamide based polymer layer obtained in the step (2) in the preparation example 4.
Comparative example 2
An antifogging coating comprises the following components in parts by weight:
the nano material is the nano zirconium phosphate coated with the N-isopropyl acrylamide based polymer layer obtained in the step (2) in the preparation example 4.
Comparative example 3
An antifogging coating which is different from the antifogging coating in example 1 only in that the fluorine-containing temperature-sensitive nano-material in the antifogging coating is replaced by the fluorine-containing nano-material provided by the comparative preparation example 1 with equal mass; other raw materials, components and preparation methods are the same as those of example 1.
The antifogging coatings provided in examples 1-10 and comparative examples 1-3 were subjected to performance tests by the following specific methods:
spraying the antifogging coating to be measured on a glass substrate, standing to enable the coating to be leveled, and irradiating and curing for 30s through an ultraviolet lamp to obtain a coating; the following performance tests were performed on it:
(1) contact angle: respectively testing the water contact angle and the oil (hexadecane) contact angle of the coating at 25 ℃ by using a contact angle measuring instrument (SDC-200S, Chengding precision instruments Ltd, Dongguan city); the coating was heated to 35 ℃ to test the oil (hexadecane) contact angle.
The coating contact angle test result graph of the antifogging coating provided by the example 1 is shown in fig. 1, the water contact angle of the antifogging coating is 0 degrees, the oil contact angle of the antifogging coating at 35 ℃ is 112.3 degrees, and the antifogging coating has super-hydrophilicity and oleophobicity; the graphs of the coating contact angle test results of the antifogging coatings provided by examples 7-10 and comparative examples 1-3 are shown in fig. 2-8, respectively; the contact angle test data for examples 1-10 and comparative examples 1-3 are shown in Table 1.
(2) Antifogging property: the coatings on the glass substrates were tested for antifogging behavior at a distance of 20cm, with steam steaming at a high temperature of 100 ℃.
(3) Antifogging and water resistance: and (3) placing the coating sample to be tested in normal-temperature deionized water for soaking for 30min, taking out the sample, drying for 1h at room temperature, and carrying out antifogging test.
Evaluation criteria for fogging:
grade 1 represents completely clear without water droplets;
grade 2 represents better transparency, a small amount of uneven large water drops exist, and the area of the water drops is not more than 5%;
grade 3 represents basic transparency, more water drops exist, and the area of the water drops does not exceed 30%;
level 4 represents translucence, a plurality of small water drops exist, and the area of the water drops is more than 50%;
level 5 represents complete opacity.
(4) Stain resistance: coating the chili oil on the surface of a coating to be tested, standing in an oven (at 35 ℃) for 1h, and observing whether the chili oil can be wiped off or not; grade 1 represents complete wiping without residue, grade 2 represents leaving about 30% light trace, grade 3 represents leaving obvious trace, and the trace area is more than 30%.
The test results are shown in table 1:
TABLE 1
According to the test results, the antifogging coating provided by the invention is prepared by compounding a specific fluorine-containing temperature-sensitive nano material, urethane acrylate and a photoinitiator to obtain a coating with a super-hydrophilic surface, wherein the water contact angle in air is less than 28 degrees, and the antifogging performance reaches level 1; and the water resistance and the stability of the coating are excellent, and the coating can still reach the level 1 antifogging performance after being soaked in water for 30min and then dried. Meanwhile, a coating formed by the antifogging coating has temperature sensitivity, the oleophobic property at room temperature (25 ℃) is not obvious, the oil contact angle is only 55-60 degrees, the polarity and the oleophobic property of the coating can be amplified at the environment temperature higher than 32 ℃, the oil contact angle on the surface is larger than 90 degrees, the oil contact angle at 35 ℃ can be larger than 110 degrees through the design of components, and the antifouling property is 1 grade, so that the antifogging effect, the antifouling effect, the stability and the reliability are achieved.
The preferable fluorine-containing temperature-sensitive nano material is obtained by reacting fluorine-containing isocyanate with a two-dimensional nano material coated with a temperature-sensitive polymer layer, and a proper amount of fluorine-containing groups are anchored and grafted on the surface of the material, so that the coating has hydrophilicity and excellent anti-fog effect, and the micro-morphology and group arrangement characteristic are changed under the stimulation of external temperature, thereby showing better oleophobic property and antifouling effect. The test result graph of the coating antifogging performance of the antifogging coatings provided by the examples 1 and 7 to 9 is shown in FIG. 9, the test result graph of the coating antifogging water resistance of the antifogging coatings provided by the examples 1, 8 and 10 is shown in FIG. 10, and the black frame positions in the graph are the areas where the coatings are located; as can be seen from the performance data shown in fig. 9, fig. 10 and table 1, compared with examples 1 to 6, the antifogging coating of example 8 has fewer fluorine-containing groups on the fluorine-containing temperature-sensitive nanomaterial, and the antifogging effect and the antifogging water resistance of the coating can meet the use requirements, but the oleophobic property and the antifouling property of the coating are reduced; the fluorine-containing temperature-sensitive nanomaterial in example 7 contains many fluorine-containing groups, so that the surface energy of the coating is low, the hydrophilicity and the antifogging performance are reduced, the coating shows water drops in an antifogging test, and the antifogging water resistance is poor.
In the invention, the specific fluorine-containing temperature-sensitive nano material is compounded with the resin, so that the coating has super-hydrophilicity and antifogging effects and has good oleophobic property and antifouling property under the stimulation of temperature; if the consumption of the fluorine-containing temperature-sensitive nano material is too much (example 10), the film forming property of the coating is poor, so that the stability of the coating is influenced; if the amount of the fluorine-containing temperature sensitive nanomaterial is too small (example 9), both the antifogging effect and antifouling property of the coating are significantly reduced. If the coating does not contain specific fluorine-containing temperature-sensitive nano materials (comparative examples 1-3), the coating lacks the synergistic effect of the temperature-sensitive polymeric layer and the fluorine-containing group grafted on the polymeric layer, so that the oil repellency and the antifouling property cannot be obtained, and the hydrophilicity and the antifogging effect of the coating are influenced.
The applicant states that the present invention is illustrated by the above examples to an antifogging coating of the present invention and its preparation method and application, but the present invention is not limited to the above process steps, i.e. it does not mean that the present invention must rely on the above process steps to be carried out. It will be apparent to those skilled in the art that any modification of the present invention, equivalent substitutions of selected materials and additions of auxiliary components, selection of specific modes and the like, which are within the scope and disclosure of the present invention, are contemplated by the present invention.
Claims (10)
1. An antifogging coating is characterized by comprising a combination of urethane acrylate, a photoinitiator and a fluorine-containing temperature-sensitive nano material;
the fluorine-containing temperature-sensitive nano material comprises a two-dimensional nano material and an N-isopropyl acrylamide-based polymer layer coated on the two-dimensional nano material; the N-isopropyl acrylamide-based polymer layer is connected with a fluorine-containing group.
2. The anti-fog coating of claim 1 wherein the two-dimensional nanomaterial comprises any one of graphene, nano-zirconium phosphate, or layered clay silicate material, or a combination of at least two thereof;
preferably, the particle size of the two-dimensional nano material is 30-3000 nm.
3. The anti-fog coating of claim 1 or 2 wherein the polymeric monomers of the N-isopropylacrylamide-based polymer layer comprise a combination of N-isopropylacrylamide and a hydroxyl-containing acrylate;
preferably, the molar ratio of the N-isopropylacrylamide to the hydroxyl-containing acrylate is (1.5-5): 1;
preferably, the hydroxyl-containing acrylate comprises any one of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, or a combination of at least two thereof.
4. The anti-fog coating of any one of claims 1-3 wherein the fluorine-containing group is attached to the N-isopropylacrylamide-based polymer layer by a urethane linkage.
5. The anti-fog coating as claimed in claim 3 or 4, wherein the fluorine-containing temperature-sensitive nanomaterial is prepared by a method comprising the steps of:
(1) treating the two-dimensional nano material by using a silane coupling agent containing alkenyl to obtain an alkenyl modified two-dimensional nano material;
(2) mixing the alkenyl modified two-dimensional nanomaterial obtained in the step (1), a polymerization monomer, a cross-linking agent and an initiator, and then reacting to obtain a two-dimensional nanomaterial coated with an N-isopropyl acrylamide based polymer layer;
(3) reacting the two-dimensional nano material obtained in the step (2) with fluorine-containing isocyanate to obtain the fluorine-containing temperature-sensitive nano material;
preferably, the alkenyl-containing silane coupling agent includes any one of a vinyl silane coupling agent, a methacrylate silane coupling agent, an allyl silane coupling agent, or an acryloxy silane coupling agent or a combination of at least two thereof;
preferably, the mass ratio of the alkenyl modified two-dimensional nano material to the polymerized monomer is 1 (1-10);
preferably, the crosslinking agent comprises N, N' -methylenebisacrylamide;
preferably, the mass ratio of the cross-linking agent to the polymerized monomer is (0.005-0.2): 1;
preferably, the initiator comprises a persulfate initiator;
preferably, the temperature of the reaction of step (2) is 50-90 ℃;
preferably, the reaction time of the step (2) is 1-12 h;
preferably, the fluorine-containing isocyanate is obtained by reacting fluorine-containing monohydric alcohol with diisocyanate;
preferably, the fluorine-containing monohydric alcohol comprises any one of trifluoroethanol, hexafluoroisopropanol, heptafluorobutanol, octafluoropentanol, nonafluorooctanol, tridecafluorooctanol or pentadecafluorooctanol or a combination of at least two of the same;
preferably, the diisocyanate comprises any one of isophorone diisocyanate, hexamethylene diisocyanate or dicyclohexylmethane diisocyanate or a combination of at least two of the isophorone diisocyanate, the hexamethylene diisocyanate or the dicyclohexylmethane diisocyanate;
preferably, the mass ratio of the two-dimensional nano material to the fluorine-containing isocyanate in the step (3) is 1 (0.1-0.7);
preferably, the temperature of the reaction in the step (3) is 20-50 ℃;
preferably, the reaction time of step (3) is 0.5-6 h.
6. The anti-fog coating of any one of claims 1-5, comprising the following components in parts by weight:
40-60 parts of urethane acrylate
0.5-10 parts of photoinitiator
8-20 parts of fluorine-containing temperature-sensitive nano material.
7. The anti-fog coating of any one of claims 1 to 6, wherein the photoinitiator comprises any one or a combination of at least two of a benzil photoinitiator, an aromatic ketone photoinitiator, an acylphosphorus oxide photoinitiator, or a benzoin photoinitiator;
preferably, the photoinitiator comprises any one of 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl acetone, 2-methyl-2- (4-morpholinyl) -1- (4- (methylthio) phenyl) -1-propanone, benzoin dimethyl ether, benzoin ethyl ether, benzoin isopropyl ether, phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide, 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide or ethyl 2,4, 6-trimethylbenzoyl phenyl phosphonate, or a combination of at least two thereof.
8. The anti-fog coating of any one of claims 1-7 further comprising a diluent;
preferably, the diluent comprises any one of water, propylene glycol methyl ether, propylene glycol ethyl ether, ethylene glycol butyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monopropyl ether, or dipropylene glycol monobutyl ether, or a combination of at least two thereof;
preferably, the amount of the diluent in the antifogging coating is 1-20 parts.
9. A method for preparing an antifog coating according to any of claims 1 to 8, characterized in that it comprises: and mixing and uniformly dispersing the urethane acrylate, the photoinitiator and the fluorine-containing temperature-sensitive nano material to obtain the antifogging coating.
10. Use of an anti-fog coating according to any one of claims 1 to 8 in a medical device;
preferably, the medical instrument comprises an endoscope or a laparoscope.
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