CN114058199B

CN114058199B - UV-cured super-hydrophilic anti-fog coating and preparation method and application thereof

Info

Publication number: CN114058199B
Application number: CN202111640947.5A
Authority: CN
Inventors: 张至; 南玉
Original assignee: Shenzhen Nanke New Material Technology Co ltd
Current assignee: Shenzhen Nanke New Material Technology Co ltd
Priority date: 2021-12-29
Filing date: 2021-12-29
Publication date: 2022-11-08
Anticipated expiration: 2041-12-29
Also published as: CN114058199A

Abstract

The invention provides a UV-cured super-hydrophilic anti-fog coating and a preparation method and application thereof. The UV-cured super-hydrophilic antifogging coating comprises the following components in parts by weight: 30-70 parts of UV resin oligomer, 20-50 parts of acrylic monomer, 10-30 parts of surfactant and 1-5 parts of modified two-dimensional nano material; the modified two-dimensional nano material comprises the following raw materials in parts by weight: 0.5-2 parts of two-dimensional nano material and 0.5-3 parts of modifier; the modifier is selected from an acrylic acid modifier or an acrylate modifier. The UV-cured super-hydrophilic antifogging coating provided by the invention has good hydrophilicity and mechanical properties, good water resistance and long-time antifogging property, and is suitable for preparing antifogging coatings or antifogging films.

Description

UV-cured super-hydrophilic anti-fog coating and preparation method and application thereof

Technical Field

The invention belongs to the technical field of coatings, and particularly relates to a UV-cured super-hydrophilic antifogging coating as well as a preparation method and an application thereof.

Background

The transparent material has a light transmittance of 80% or more with respect to visible light having a wavelength of 400 to 800 nm. Glass is the most commonly used inorganic transparent material. In the daily use process, the surface of the glass is easy to be atomized and dewed, thereby influencing the use of the glass. The fogging phenomenon of glass brings a lot of troubles to people and even can cause huge economic loss to people. For example, in cold seasons with low air temperature, the fogging of the glasses and various protective masks affects the sight of people, thereby obstructing people's travel; the fogging of the windshield of the automobile can cause great potential safety hazard to people in driving; as another example, when a mist droplet is condensed on the lens surface of a precision analysis instrument such as an infrared optical microscope, the accuracy of its analysis may be reduced; when the fog drops are condensed on the light-transmitting plate of the solar cell, the solar energy absorption efficiency is reduced, so that the solar cell equipment is not favorable for fully playing the due role. Therefore, it is a very important subject to be studied to prevent fogging and condensation of glass.

The antifogging material is a functional coating for slowing down or preventing the fogging or dewing phenomenon on the surface of the transparent substrate. Generally, antifogging coatings are mainly classified into inorganic-system antifogging coatings, organic-system antifogging coatings, and organic-inorganic hybrid-system antifogging coatings. Surface coating with anti-fogging coatings is a more common method for eliminating fogging: firstly, the hydrophilic polymer coating is used, so that the contact angle (theta) of water on the surface of the material is reduced, the water is spread and thinned, the diffuse reflection is reduced, light rays can well penetrate through the material, but the hydrophilic polymer coating can form hydrogen bonds or stronger polar bonds, the room temperature viscosity is higher, the leveling property is poor, the uniform spreading is not easy, and the corrosion resistance is also poor; secondly, the hydrophobic polymer coating is used to increase the contact angle of water on the surface of the material, and after water drops form water drops, the water drops are difficult to stay on the surface due to the action of gravity, so as to achieve the anti-fog purpose.

CN112680103A discloses an ultrahigh-strength hydrophobic antifogging coating composition and an application thereof. The antifogging coating composition is prepared from the following raw materials in parts by weight: 100 parts of resin-based polymerization monomer, 1-3 parts of modified silicon carbide whisker, 1-3 parts of photoinitiator, 0.1-0.3 part of flatting agent and 0.3-0.5 part of defoaming agent; the resin matrix comprises 60-80 parts of silicon acrylate oligomer and 20-40 parts of silicon acrylate monomer. According to the technical scheme, the mixture of the silicon-containing acrylate oligomer and the silicon-containing acrylate monomer is used as the polymerization monomer, the prepared composition has excellent water resistance, light resistance and hydrophobicity, and the modified silicon carbide crystal whisker is added to play an excellent mechanical property enhancing role, so that the cured coating has ultrahigh strength, scratch resistance and hydrophobicity, but the antifogging property is poor, if extremely small water drops in fog are encountered, when the surface acting force between the water drops and the coating is greater than the self gravity, the antifogging effect cannot be achieved.

CN111849333A discloses SiO ₂ A preparation method of hydrophilic modified UV-cured waterborne polyurethane antifogging coating. The preparation method comprises the following steps: firstly, synthesizing waterborne polyurethane, then preparing nano silica sol by hydrolyzing tetraethoxysilane TEOS, finally introducing the nano silica sol into the waterborne polyurethane to generate a cross-linking structure in situ, and curing to obtain SiO ₂ Hydrophilic modified UV-cured waterborne polyurethane antifogging coating. This techniqueSiO prepared by scheme ₂ The hydrophilic modified UV-cured waterborne polyurethane antifogging coating has good hydrophilicity, weather resistance and wear resistance, but has poor water resistance.

CN106752857A discloses a preparation method of a dual-curing acrylate super-hydrophilic antifogging coating. According to the preparation method, acrylate monomers are used as main raw materials, a silane coupling agent, hydroxyethyl acrylate and a sulfonic acrylamide monomer are introduced by adopting free radical polymerization, and double bonds are introduced by adopting half-terminated polyurethane and hydroxyl in a main chain to react. Wherein the sulfonic acid group on the main chain can endow the coating film with good hydrophilicity; the silane coupling agent and the tetraethoxysilane can be hydrolyzed and cured to form a coating, and meanwhile, the non-condensed silicon hydroxyl can further improve the hydrophilicity of the coating and endow the coating with good antifogging performance; the introduction of double bonds enables the photocuring of acrylates. The coating prepared by the technical scheme has better hydrophilicity.

In the prior art, the hydrophilic polymer coating may form hydrogen bonds or stronger polar bonds, has higher room-temperature viscosity, poor leveling property, difficult uniform spreading and poor corrosion resistance, and the prepared hydrophilic polymer coating has poor water resistance and short antifogging time. Therefore, how to provide a coating with good hydrophilicity, good water resistance and durable antifogging effect is a technical problem to be solved at present.

Disclosure of Invention

Aiming at the defects of the prior art, the invention aims to provide a UV-cured super-hydrophilic antifogging coating, and a preparation method and application thereof. According to the invention, through the design of raw material components in the UV-cured super-hydrophilic anti-fog coating and the matched use of the surfactant and the modified two-dimensional nano material, the surfactant can be uniformly dispersed in the anti-fog coating, so that the prepared anti-fog coating has better water resistance and longer-time anti-fog effect.

In order to achieve the purpose, the invention adopts the following technical scheme:

in a first aspect, the invention provides a UV-cured super-hydrophilic anti-fog coating, which comprises the following components in parts by weight:

30-70 parts of UV resin oligomer, 20-50 parts of acrylic monomer, 10-30 parts of surfactant and 1-5 parts of modified two-dimensional nano material;

the modified two-dimensional nano material comprises the following raw materials in parts by weight: 0.5-2 parts of two-dimensional nano material and 0.5-3 parts of modifier;

the modifier is selected from an acrylic acid modifier or an acrylate modifier.

In the prior art, the antifogging coating prepared by the hydrophilic antifogging coating has a good antifogging effect because a surfactant in the antifogging coating can move and migrate in the coating and is enriched on the surface of the coating, so that the coating has good hydrophilicity, the contact angle of water on the surface of the coating can be reduced, the water is spread and thinned, and the antifogging effect is achieved. However, when the surfactant is concentrated on the surface of the coating, the surfactant is separated from the coating along with the movement of the water film, so that the coating loses the antifogging effect. Therefore, the hydrophilic antifogging coating has poor water resistance and short antifogging time.

According to the invention, the two-dimensional nanomaterial is modified by the modifier, so that the surface of the two-dimensional nanomaterial contains carbon-carbon double bonds, and the modified two-dimensional nanomaterial can carry out polymerization reaction with UV resin oligomer and acrylic monomer to form an antifogging coating when the antifogging coating is prepared subsequently. Therefore, the modified two-dimensional nano material can be stably and uniformly dispersed in the coating. Meanwhile, the surfactant and the modified two-dimensional nano material are matched for use, and the surfactant is further uniformly dispersed on the surface or in the modified two-dimensional nano material, so that the surfactant is uniformly dispersed in the coating along with the modified two-dimensional nano material, and the coating has better hydrophilicity; on the other hand, the modified two-dimensional nano material can slow down the motion and the migration of the surfactant in the coating, so that the coating has better hydrophilicity, better water resistance and better antifogging durability.

The modified two-dimensional nano material exists as a bridge connecting the surfactant and a coating matrix (namely UV resin oligomer and acrylic monomer), the surfactant can be uniformly dispersed in the coating matrix through the modified two-dimensional nano material, and the motion of the surfactant in a coating can be slowed down by the existence of the modified two-dimensional nano material, so that the UV-cured super-hydrophilic antifogging coating has good hydrophilicity, good water resistance and a long-time antifogging effect.

In the present invention, the weight part of the UV resin oligomer may be 30 parts, 35 parts, 40 parts, 45 parts, 50 parts, 55 parts, 60 parts, 65 parts, 70 parts, or the like.

The acrylic monomer may be present in an amount of 20 parts, 22 parts, 25 parts, 27 parts, 30 parts, 33 parts, 36 parts, 39 parts, 42 parts, 46 parts, 50 parts, or the like by weight.

The weight portion of the surfactant can be 10 parts, 12 parts, 14 parts, 16 parts, 18 parts, 20 parts, 22 parts, 24 parts, 26 parts, 28 parts, 30 parts, or the like.

The modified two-dimensional nano material can be 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts or 5 parts by weight and the like.

The weight portion of the two-dimensional nano material can be 0.5 portion, 0.6 portion, 0.8 portion, 1 portion, 1.2 portions, 1.4 portions, 1.6 portions, 1.8 portions or 2 portions, etc.

The modifier may be present in an amount of 0.5 parts, 0.6 parts, 0.8 parts, 1 part, 1.2 parts, 1.4 parts, 1.6 parts, 1.8 parts, 2 parts, 2.2 parts, 2.4 parts, 2.6 parts, 2.8 parts, 3 parts, or the like.

The following is a preferred technical solution of the present invention, but not a limitation to the technical solution provided by the present invention, and the object and advantageous effects of the present invention can be better achieved and achieved by the following preferred technical solution.

As a preferable technical scheme of the invention, the two-dimensional nano material is selected from any one or a combination of at least two of nano zirconium phosphate, modified graphene, montmorillonite, talcum powder or titanium dioxide nanosheets.

Preferably, the modified graphene is selected from graphene oxide and/or fluorinated graphene oxide.

Preferably, D of the two-dimensional nanomaterial ₉₀ The particle diameter is 30 to 5000nm (for example, 30nm, 50nm, 100nm, 200nm, 500nm, 1000nm, 1500nm, 2000nm, 2500nm, 3000 nm, 3500nm, 4000nm, 4500nm or 5000nm, etc.), and more preferably 50 to 2000nm.

In the invention, the prepared antifogging coating has better water resistance and longer-time antifogging effect by controlling the particle size of the two-dimensional nano material within a specific range. If the particle size of the two-dimensional nano material is too small, the water resistance of the prepared antifogging coating is poor; if the particle size of the two-dimensional nano material is too large, the antifogging property of the antifogging coating is poor due to the blocking property of the two-dimensional nano material.

Preferably, the acrylic modifier is selected from any one or a combination of at least two of acrylic acid, acetaminoacrylic acid, phenylacrylic acid, imidazoleacrylic acid, pyridineacrylic acid, terephthalcrylic acid, ethoxybenzoylacrylic acid, acetaminoacrylic acid, thiopheneacrylic acid, furanpropenoic acid, or the like.

Preferably, the acrylate modifier is selected from any one of methyl methacrylate, ethyl methacrylate, butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, isobutyl acrylate or tert-butyl acrylate or a combination of at least two thereof.

Preferably, the raw material for preparing the modified two-dimensional nano material also comprises 0.01-0.1 part of catalyst, such as 0.01 part, 0.02 part, 0.03 part, 0.04 part, 0.05 part, 0.06 part, 0.07 part, 0.08 part, 0.09 part or 0.1 part, etc.

Preferably, the catalyst is selected from any one of concentrated sulfuric acid, p-toluenesulfonic acid, tetrabutyltin or methanesulfonic acid or a combination of at least two thereof.

In the invention, the concentrated sulfuric acid is a concentrated sulfuric acid solution with the mass percentage of 98%.

Preferably, the raw materials for preparing the modified two-dimensional nanomaterial further comprise 20-30 parts of a solvent, which can be, for example, 21 parts, 22 parts, 23 parts, 24 parts, 25 parts, 26 parts, 27 parts, 28 parts, 29 parts or 30 parts.

Preferably, the solvent is selected from any one of deionized water, ethanol, isopropanol or toluene or a combination of at least two thereof.

Preferably, the raw material for preparing the modified two-dimensional nanomaterial further comprises 0.5-2 parts of silane coupling agent, such as 0.5 part, 0.6 part, 0.8 part, 1 part, 1.2 parts, 1.4 parts, 1.6 parts, 1.8 parts, 2 parts and the like.

Preferably, the silane coupling agent is selected from any one of or a combination of at least two of vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris (methoxyethoxy) silane, methacryloxypropyltriethoxysilane, 3- (methacryloxy) propyltrimethoxysilane or 3-methacryloxypropylmethyldimethoxysilane.

As a preferable technical scheme of the invention, the preparation method of the modified two-dimensional nano material is selected from the method A or the method B.

The method A comprises the following steps:

and (2) uniformly mixing the two-dimensional nano material with a solvent, adding an acrylic acid modifier and a catalyst into the mixture, and carrying out modification reaction to obtain the modified two-dimensional nano material.

The method B comprises the following steps:

(1) Mixing a two-dimensional nano material, a silane coupling agent and a solvent, and reacting to obtain a mixture A;

(2) And (2) adding an acrylate modifier and a catalyst into the mixture A obtained in the step (1) for modification reaction to obtain the modified two-dimensional nano material.

As a preferred embodiment of the present invention, the temperature of the modification reaction in the method A is 70 to 90 ℃ and may be, for example, 70 ℃, 72 ℃, 74 ℃, 76 ℃, 78 ℃, 80 ℃, 82 ℃, 84 ℃, 86 ℃, 88 ℃ or 90 ℃.

The modification reaction time in the method A is preferably 3 to 8 hours, and may be, for example, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, or the like.

Preferably, the method A further comprises a post-treatment step after the modification reaction is completed.

Preferably, the post-treatment method comprises suction filtration, cleaning and drying.

As a preferred embodiment of the present invention, the temperature of the reaction in the step (1) is 50 to 80 ℃ and may be, for example, 50 ℃, 52 ℃, 55 ℃, 57 ℃, 60 ℃, 63 ℃, 66 ℃, 69 ℃, 72 ℃, 75 ℃, 78 ℃ or 80 ℃.

Preferably, the reaction time in step (1) is 0.5 to 3 hours, and may be, for example, 0.5 hour, 1 hour, 1.5 hour, 2 hours, 2.5 hours, 3 hours, or the like.

Preferably, the reaction temperature in step (2) is 50 to 80 ℃, for example, 50 ℃, 52 ℃, 55 ℃, 57 ℃, 60 ℃, 63 ℃, 66 ℃, 70 ℃, 72 ℃, 75 ℃, 77 ℃ or 80 ℃.

Preferably, the time of the modification reaction in the step (2) is 1 to 5 hours, and for example, 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, or the like can be used.

Preferably, the modification reaction in the step (2) is completed and then a post-treatment step is included.

In a preferred embodiment of the present invention, the number average molecular weight of the UV resin oligomer is 1000 to 3000, and may be, for example, 1000, 1200, 1400, 1600, 1800, 2000, 2200, 2400, 2600, 2800, 3000, or the like.

Preferably, the acrylic monomer is selected from any one of acrylic acid, methyl methacrylate, ethyl methacrylate, butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, isobornyl methacrylate, dicyclopentadiene acrylate, trimethylol cyclohexyl acrylate, hydroxybutyl acrylate or phenoxyethyl acrylate or a combination of at least two thereof.

Preferably, the surfactant is selected from any one or a combination of at least two of polyether modified polydimethylsiloxane, polyester modified polydimethylsiloxane, perfluoroalkyl polyoxyethylene ether, long-chain fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene ether, fatty acid polyoxyethylene ester, polyoxyethylene alkylamine and polyoxyethylene alkylolamide.

In a preferred embodiment of the present invention, the UV-curable super-hydrophilic antifogging coating further comprises 2 to 6 parts of photoinitiator, which may be, for example, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts, 5.5 parts, or 6 parts.

Preferably, the photoinitiator is selected from any one of or a combination of at least two of photoinitiator 1173, photoinitiator 184, photoinitiator TPO-L, or photoinitiator 819.

It is to be noted that the photoinitiator 1173 is 2-hydroxy-2-methyl-1-phenylpropanone, the photoinitiator 184 is 1-hydroxycyclohexyl phenyl ketone, the photoinitiator TPO is 4, 6-trimethylbenzoyl-diphenylphosphine oxide, the photoinitiator TPO-L is ethyl 2,4, 6-trimethylbenzoylphenylphosphinate, and the photoinitiator 819 is phenylbis (2, 4, 6-trimethylbenzoyl) phosphine oxide.

In a second aspect, the present invention provides a preparation method of the UV-curable superhydrophilic anti-fog coating according to the first aspect, the preparation method comprising the following steps:

(A) Mixing the modified two-dimensional nano material with a surfactant to obtain a mixture;

(B) And (2) uniformly mixing the mixture obtained in the step (A) with a UV resin oligomer, an acrylic monomer, a photoinitiator and an optional organic solvent to obtain the UV-cured super-hydrophilic antifogging coating.

According to the invention, the surfactant is uniformly dispersed on the surface and inside of the modified two-dimensional nanomaterial by mixing the modified two-dimensional nanomaterial with the surfactant and then mixing the surfactant with other components, so that the migration and loss of the surfactant in the anti-fog coating are slowed down, and the anti-fog coating has good water resistance and a long-time anti-fog effect.

As a preferred embodiment of the present invention, the temperature of the mixing in the step (A) is 50 to 80 ℃ and may be, for example, 50 ℃, 52 ℃, 55 ℃, 57 ℃, 60 ℃, 63 ℃, 66 ℃, 69 ℃, 72 ℃, 75 ℃, 78 ℃ or 80 ℃.

Preferably, the mixing time in step (A) is more than or equal to 1h, and can be 1h, 2h, 3h, 4h, 5h or the like.

In a third aspect, the present invention provides a use of the UV-curable superhydrophilic anti-fog coating according to the first aspect in an anti-fog coating or an anti-fog film.

Compared with the prior art, the invention has the following beneficial effects:

according to the invention, through the design of the components of the UV-cured super-hydrophilic anti-fog coating, the surfactant and the modified two-dimensional nano material are further used in a matched manner, the particle size of the two-dimensional nano material is controlled within a specific range, and meanwhile, through a specific preparation method, the prepared UV-cured super-hydrophilic anti-fog coating has good hydrophilicity and good mechanical properties, after an anti-fog test, the anti-fog effect is 1 grade, and after an anti-fog durability test is performed on an anti-fog film prepared from the UV-cured super-hydrophilic anti-fog coating at 50 ℃ and 100 ℃, the anti-fog durability is 1 grade, the anti-fog friction resistance is more than 10 times, specifically 10-12 times, the water resistance is 1 grade, the water contact angle is 0 degree, the adhesive force is 0 grade, the hardness is 2-3H, and the light transmittance is 92.0-94.0%.

Drawings

FIGS. 1 to 9 are photographs of antifogging tests performed on antifogging films prepared from the UV-curable super-hydrophilic antifogging coatings provided in examples 1, 5 to 9 and comparative examples 1 to 3, respectively;

FIGS. 10 to 14 are photographs of water resistance tests performed on antifogging films prepared from the UV-curable super-hydrophilic antifogging coatings provided in example 1, example 7, example 9, comparative example 1 and comparative example 3, respectively;

FIGS. 15-16 are photographs of the antifogging films prepared from the UV-curable super-hydrophilic antifogging coatings provided in examples 1 and 7 after rubbing for 2 times, respectively;

FIGS. 17 to 18 are photographs of the antifogging films prepared from the UV curable super hydrophilic antifogging coatings provided in examples 1 and 7 after 10 times of rubbing;

FIG. 19 is a test photograph of an anti-fog film prepared from the UV-curable super-hydrophilic anti-fog coating provided in example 9 after being rubbed 1 time respectively;

FIGS. 20 to 27 are photographs of antifogging durability tests performed on antifogging films prepared from the UV-curable super-hydrophilic antifogging coatings provided in examples 1, 5 to 7, 9 and comparative examples 1 to 3 under boiling water condition at 100 deg.C, respectively;

FIGS. 28 to 30 are photographs of the water contact angle of the antifogging films prepared from the UV-curable super-hydrophilic antifogging coatings provided in example 1, example 8 and comparative example 2, respectively;

wherein, 1 is an antifogging film.

Detailed Description

The technical scheme of the invention is further explained by the specific implementation mode in combination with the attached drawings. 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 limitation of the present invention.

Some of the component sources in the following examples and comparative examples are as follows:

UV resin oligomer: wuxi Weidu electronics materials, inc.;

and (3) graphene oxide: liaoning Lanjing technologies, inc.;

montmorillonite: beijing Yiyu specialization science and technology development Co;

talc powder: yikou magnesium Union mining Co., ltd;

nano zirconium phosphate: prepared by the method of CN 108129927B;

polyether-modified polydimethylsiloxane: german Bike;

polyester-modified polydimethylsiloxane: german Bike;

perfluoroalkyl polyoxyethylene ether: kemu chemistry;

alkylphenol ethoxylates: shenzhen Jitian chemical industry Co.

Example 1

The embodiment provides a UV-cured super-hydrophilic antifogging coating and a preparation method thereof, wherein the UV-cured super-hydrophilic antifogging coating comprises the following components in parts by weight:

50 parts of UV resin oligomer, 40 parts of acrylic acid, 20 parts of polyether modified polydimethylsiloxane, 4.5 parts of modified two-dimensional nano material and 1173 parts of photoinitiator;

the modified two-dimensional nano material comprises the following raw materials in parts by weight: nano zirconium phosphate (D) ₉₀ Particle size of 200 nm) 1.2 parts, methyl methacrylate 1.8 parts, vinyltriethoxysilane 1.5 parts, tetrabutyltin 0.05 parts and ethanol 25 parts;

the preparation method of the modified two-dimensional nano material comprises the following steps:

(1) Mixing nano zirconium phosphate, vinyl triethoxysilane and ethanol at 70 ℃ and reacting for 3h to obtain a mixture A;

(2) Adding methyl methacrylate and tetrabutyltin into the mixture A obtained in the step (1) at 80 ℃, carrying out modification reaction for 4 hours, carrying out suction filtration, cleaning and drying to obtain the modified two-dimensional nano material.

The preparation method of the UV-cured super-hydrophilic antifogging coating comprises the following steps:

(A) Mixing the modified two-dimensional nano material with polyether modified polydimethylsiloxane for 2 hours at 60 ℃ to obtain a mixture;

(B) And (2) uniformly mixing the mixture obtained in the step (A) with a UV resin oligomer, acrylic acid and a photoinitiator 1173 to obtain the UV-cured super-hydrophilic antifogging coating.

Example 2

70 parts of UV resin oligomer, 20 parts of methyl methacrylate, 30 parts of polyester modified polydimethylsiloxane, 5 parts of modified two-dimensional nano material and 184 parts of photoinitiator;

the modified two-dimensional nano material comprises the following raw materials in parts by weight: graphene oxide (D) ₉₀ Particle size 2000 nm) 2 parts, ethyl methacrylate 2 parts, vinyl trimethoxy silane 1 part, p-toluenesulfonic acid 0.1 part and isopropanol 30 parts;

(1) Mixing graphene oxide, vinyl trimethoxy silane and isopropanol at 80 ℃ and reacting for 3h to obtain a mixture A;

(2) Adding ethyl methacrylate and p-toluenesulfonic acid into the mixture A obtained in the step (1) at 90 ℃, performing modification reaction for 2 hours, and performing suction filtration, cleaning and drying to obtain the modified two-dimensional nano material.

(A) Mixing the modified two-dimensional nano material with polyester modified polydimethylsiloxane for 1h at 80 ℃ to obtain a mixture;

(B) And (2) uniformly mixing the mixture obtained in the step (A) with a UV resin oligomer, methyl methacrylate and a photoinitiator 184 to obtain the UV-cured super-hydrophilic antifogging coating.

Example 3

30 parts of UV resin oligomer, 50 parts of butyl methacrylate, 10 parts of perfluoroalkyl polyoxyethylene ether, 1 part of modified two-dimensional nano material and 2 parts of photoinitiator TPO;

the modified two-dimensional nano material comprises the following raw materials in parts by weight: talcum powder (D) ₉₀ Particle size 50 nm), 0.5 part of acrylic acid, 0.01 part of methanesulfonic acid and 20 parts of ethanol;

uniformly mixing talcum powder and ethanol at 70 ℃, adding acrylic acid and methanesulfonic acid, carrying out modification reaction for 8 hours, carrying out suction filtration, cleaning and drying to obtain the modified two-dimensional nano material;

(A) Mixing the modified two-dimensional nano material with perfluoroalkyl polyoxyethylene ether for 3 hours at 50 ℃ to obtain a mixture;

(B) And (2) uniformly mixing the mixture obtained in the step (A) with a UV resin oligomer, butyl methacrylate and a photoinitiator TPO to obtain the UV-cured super-hydrophilic antifogging coating.

Example 4

60 parts of UV resin oligomer, 30 parts of methyl acrylate, 15 parts of alkylphenol polyoxyethylene, 4 parts of modified two-dimensional nano material and 819 3 parts of photoinitiator;

the modified two-dimensional nano material comprises the following raw materials in parts by weight: montmorillonite (D) ₉₀ Particle size 5000 nm) 1 part, p-phenylene diacrylate 3 parts, p-toluenesulfonic acid 0.02 part and ethanol 22 parts;

uniformly mixing montmorillonite and ethanol at 80 ℃, adding paraphenylacrylic acid and paratoluenesulfonic acid, performing modification reaction for 3 hours, and performing suction filtration, cleaning and drying to obtain the modified two-dimensional nano material;

(A) Mixing the modified two-dimensional nano material with alkylphenol ethoxylates for 2 hours at 65 ℃ to obtain a mixture;

(B) And (2) uniformly mixing the mixture obtained in the step (A) with a UV resin oligomer, methyl acrylate and a photoinitiator 819 to obtain the UV-cured super-hydrophilic antifogging coating.

Example 5

This example provides a UV-curable super-hydrophilic anti-fog coating and a preparation method thereof, which is different from example 1 only in that D ₉₀ The nano zirconium phosphate with the particle diameter of 200nm is replaced by D ₉₀ The other conditions were the same as in example 1 except that the nano-zirconium phosphate having a particle size of 30nm was used.

Example 6

This example provides a UV-curable super-hydrophilic anti-fog coating and a preparation method thereof, which is different from example 1 only in that D ₉₀ The nano zirconium phosphate with the grain diameter of 200nm is replaced by D ₉₀ Nano zirconium phosphate with grain size of 5000nm, other conditions andthe same applies to example 1.

Example 7

This example provides a UV-curable super-hydrophilic anti-fog coating and a preparation method thereof, which is different from example 1 only in that D ₉₀ The nano zirconium phosphate with the particle diameter of 200nm is replaced by D ₉₀ The other conditions were the same as in example 1 except that the nano-zirconium phosphate had a particle size of 20 nm.

Example 8

This example provides a UV-curable super-hydrophilic anti-fog coating and a preparation method thereof, which is different from example 1 only in that D ₉₀ The nano zirconium phosphate with the grain diameter of 200nm is replaced by D ₉₀ The other conditions were the same as in example 1, except for the nano zirconium phosphate having a particle size of 6000 nm.

Example 9

This example provides a UV-curable super-hydrophilic anti-fog coating and a preparation method thereof, which are different from example 1 only in that:

uniformly mixing all components of the UV-cured super-hydrophilic antifogging coating together to obtain the UV-cured super-hydrophilic antifogging coating;

other conditions were the same as in example 1.

Comparative example 1

The comparison example provides a UV-cured super-hydrophilic anti-fog coating and a preparation method thereof, and the UV-cured super-hydrophilic anti-fog coating is different from the example 1 only in that the UV-cured super-hydrophilic anti-fog coating does not contain a modified two-dimensional nano material, and other conditions are the same as those of the example 1.

Comparative example 2

The comparative example provides a UV-cured super-hydrophilic anti-fog coating and a preparation method thereof, and the difference from the example 1 is that the UV-cured super-hydrophilic anti-fog coating does not contain polyether modified polydimethylsiloxane, and other conditions are the same as those in the example 1.

Comparative example 3

The comparison example provides a UV-cured super-hydrophilic anti-fog coating and a preparation method thereof, and the difference from the example 1 is that the two-dimensional nano material is not subjected to modification treatment, and the modified two-dimensional nano material4.5 parts of nano zirconium phosphate (D) ₉₀ Particle diameter of 200 nm) 1.2 parts, methyl methacrylate 1.8 parts, and vinyltriethoxysilane 1.5 parts, except for the same conditions as in example 1.

The UV-cured super-hydrophilic antifogging coating provided by the above examples and comparative examples is coated on a PET release film, the PET release film is removed by irradiating the PET release film for 30s with ultraviolet light to obtain an antifogging film with the thickness of 200 μm, and the performance of the antifogging film is tested by the following test method:

antifogging property: respectively sticking antifogging films prepared by the UV-cured super-hydrophilic antifogging coatings provided by the above examples and comparative examples on glass, carrying out steam spraying at a high temperature of 100 ℃ at a distance of 20cm from a sample, and observing whether the antifogging films are fogged or not;

anti-fog durability: adding 200mL of water into a beaker with the volume of 250mL, covering the cup mouth with an antifogging film prepared by using the UV-cured super-hydrophilic antifogging coating provided by the above example and comparative example, placing the beaker in a constant-temperature water bath kettle at 50 ℃, and observing the fogging condition of the antifogging film visually after 30 min; adding 500mL of water into a beaker with the volume of 1000mL, covering the cup mouth with an antifogging film prepared by respectively using the UV-cured super-hydrophilic antifogging coating provided by the above example and comparative example, placing the beaker on a heating plate, continuously boiling the water, and observing the fogging condition of the antifogging film by visual observation after 30 min;

antifogging and antifriction: the antifogging films prepared by the UV curing super-hydrophilic antifogging coatings provided by the embodiments and the comparative examples are adhered on glass, the samples are rubbed by fingers for 5 times back and forth, then the samples are steamed for 5 seconds by high-temperature steam at 100 ℃ at a position 10cm away from the antifogging films, after the antifogging effect is observed, the tests of rubbing by fingers for 1 time, steaming for 5 seconds and observing the antifogging effect are carried out at the same position, and the times of rubbing by fingers when water drops and mist appear at the same position of the samples are tested and recorded in a circulating manner;

and (3) testing water resistance: placing the antifogging films prepared by the UV-cured super-hydrophilic antifogging coatings provided by the above examples and comparative examples in deionized water at normal temperature for soaking for 30min, taking out the antifogging films, drying at room temperature for 1 hour, and performing antifogging test;

water contact angle: measuring the water drop contact angle of the antifogging film prepared by the cured super-hydrophilic antifogging coating provided by the UV in the example and the comparative example by adopting contact angle measuring instrument (model SDC-200S) of Sandingding precision instruments Limited in Dongguan city;

adhesion force: GB/T9286-1998;

hardness: after the antifogging films prepared by the UV-cured super-hydrophilic antifogging coatings provided by the above examples and comparative examples are completely cured by irradiating for 30s under ultraviolet light, a 3cm length is drawn on a paint film at an oblique angle of 45 degrees for 5 times by a force of 1 kg of vertical pressure, the paint film has no scratch, the pencil-grade hardness is the paint film hardness, wherein the pencil hardness is respectively 6B, 5B, 4B, 3B, 2B, HB, F, H, 2H, 3H, 4H, 5H, 6H, 7H, 8H and 9H;

light transmittance: cutting the antifogging films prepared from the UV-cured super-hydrophilic antifogging coatings provided by the above examples and comparative examples into squares of 5cm × 5cm by using a light transmittance haze tester, selecting the center and four vertexes of a sample to respectively test light transmittance, and taking the average value of the light transmittance to be a light transmittance value;

wherein the fogging evaluation criteria are as follows:

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 does not exceed 5%;

grade 3 represents substantially transparent, with more water droplets, the area of water droplets present not exceeding 30%;

grade 4 represents translucency, with many small water droplets, and the area of the water droplets is more than 50%;

a rating of 5 represents complete opacity.

The photographs of antifogging property test of the antifogging film 1 prepared from the UV-curable super-hydrophilic antifogging coatings provided in examples 1, 5 to 9 and comparative examples 1 to 3 are shown in fig. 1 to 9. As can be seen from fig. 1 to 9, if the particle size of the two-dimensional nanomaterial is too large (example 8, fig. 5) or the modified two-dimensional nanomaterial is not mixed with a surfactant in advance (example 9, fig. 6) or the UV-curable superhydrophilic antifogging coating does not contain a surfactant (comparative example 2, fig. 8), the antifogging property is poor.

Photographs of the water resistance test of the antifogging films 1 prepared from the UV-curable superhydrophilic antifogging coatings provided in example 1, example 7, example 9, comparative example 1, and comparative example 3 are shown in fig. 10 to 14. As can be seen from fig. 10 to 14, if the particle size of the two-dimensional nanomaterial is too small (example 7, fig. 11) or the modified two-dimensional nanomaterial is not mixed with a surfactant in advance (example 9, fig. 12) or the UV-curable superhydrophilic antifogging coating does not contain the modified two-dimensional nanomaterial (comparative example 1, fig. 13) or the two-dimensional nanomaterial in the UV-curable superhydrophilic antifogging coating is not modified (comparative example 3, fig. 14), the water resistance is poor.

Test photographs of the antifogging films prepared by the UV-cured super-hydrophilic antifogging coatings provided in the examples 1 and 7 after being rubbed for 2 times are shown in FIGS. 15-16, and it can be seen from FIGS. 15-16 that the antifogging property is better after being rubbed for 2 times; the test photographs of the antifogging films 1 prepared from the UV-curable super-hydrophilic antifogging coatings provided in examples 1 and 7 after being rubbed 10 times are shown in fig. 17-18, and it can be seen from fig. 17-18 that if the particle size of the two-dimensional nanomaterial is too small (example 7, fig. 18), the antifogging property is poor after being rubbed 10 times. Fig. 19 shows a test photograph of the antifogging film prepared from the UV-curable super-hydrophilic antifogging coating provided in example 9 after 1 rubbing, and as can be seen from fig. 19, after 1 rubbing, water marks appear on the surface of the antifogging film.

The photographs of the antifogging films 1 prepared from the UV-curable superhydrophilic antifogging coatings provided in examples 1, 5-7, 9 and comparative examples 1-3, which were subjected to the antifogging durability test under boiling water condition at 100 ℃, are shown in fig. 20-27. As can be seen from fig. 20 to 27, if the particle size of the two-dimensional nanomaterial is too small (example 7, fig. 23) or the modified two-dimensional nanomaterial is not mixed with a surfactant in advance (example 9, fig. 24) or the UV-curable superhydrophilic antifogging coating does not contain the modified two-dimensional nanomaterial (comparative example 1, fig. 25) or the UV-curable superhydrophilic antifogging coating does not contain a surfactant (comparative example 2, fig. 26) or the two-dimensional nanomaterial in the UV-curable superhydrophilic antifogging coating is not modified (comparative example 3, fig. 27), the antifogging durability is poor.

The photographs of the antifogging film 1 prepared from the UV-curable superhydrophilic antifogging coating provided in example 1, example 8 and comparative example 2, subjected to the water contact angle test, are shown in fig. 28-30. As can be seen from fig. 28 to 30, if the particle size of the two-dimensional nanomaterial is too large (example 8, fig. 29) or the UV-curable superhydrophilic antifogging coating does not contain a surfactant (comparative example 2, fig. 30), the hydrophilicity is poor.

The performance test results of the UV-curable super-hydrophilic anti-fog coating provided in the above examples and comparative examples are specifically shown in table 1 below:

TABLE 1

The contents in table 1 show that the UV-cured super-hydrophilic anti-fog coating prepared by the invention has good hydrophilicity and good mechanical properties through the design of components of the UV-cured super-hydrophilic anti-fog coating and the further matched use of the surfactant and the modified two-dimensional nano material, after an anti-fog test, the anti-fog effect is 1 grade, and after the anti-fog durability test is performed on an anti-fog film prepared from the UV-cured super-hydrophilic anti-fog coating at 50 ℃ and 100 ℃, the anti-fog durability test is 1 grade, the anti-fog friction resistance is 10-12 times, the water resistance is 1 grade, the water contact angle is 0 degree, the adhesion force is 0 grade, the hardness is 2-3H, and the light transmittance is 92.0% -94.0%.

Compared with example 1, if the particle size of the two-dimensional nano material is too small (example 7) or the particle size of the two-dimensional nano material is too large (example 8), the antifogging performance of the prepared UV-cured super-hydrophilic antifogging coating is poor. Therefore, the super-hydrophilic anti-fog coating prepared by controlling the particle size of the two-dimensional nano material within a specific range has water resistance and a good anti-fog effect.

Compared with example 1, if the surfactant and the modified two-dimensional nano material are not mixed firstly (example 9), the prepared UV-cured super-hydrophilic anti-fog coating has poor anti-fog effect.

Compared with example 1, if the UV-cured super-hydrophilic anti-fog coating does not contain the modified two-dimensional nano material (comparative example 1), the prepared UV-cured super-hydrophilic anti-fog coating has shorter anti-fog effect time; if the UV-cured super-hydrophilic antifogging coating does not contain the surfactant (comparative example 2), the prepared UV-cured super-hydrophilic antifogging coating has poor hydrophilicity; if the two-dimensional nano material is not modified (comparative example 3), the prepared UV-cured super-hydrophilic antifogging coating has a short antifogging effect time. Therefore, the UV-cured super-hydrophilic antifogging coating prepared by the method has good hydrophilicity, good water resistance and a long-term antifogging effect through the design of the components of the UV-cured super-hydrophilic antifogging coating.

In conclusion, the UV-cured super-hydrophilic antifogging coating prepared by the method has good hydrophilicity, good mechanical property, good water resistance and good antifogging durability through the design of the components of the UV-cured super-hydrophilic antifogging coating, the matched use of the surfactant and the modified two-dimensional nano material and the control of the particle size of the two-dimensional nano material in a specific range.

The applicant states that the present invention is illustrated by the detailed process flow of the present invention through the above examples, but the present invention is not limited to the above detailed process flow, that is, it does not mean that the present invention must rely on the above detailed process flow to be implemented. It should be understood by those skilled in the art that any modifications of the present invention, equivalent substitutions of the raw materials of the product of the present invention, and the addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.

Claims

1. The UV-cured super-hydrophilic antifogging coating is characterized by comprising the following components in parts by weight:

the modified two-dimensional nano material comprises the following raw materials in parts by weight: 0.5 to 2 parts of two-dimensional nano material and 0.5 to 3 parts of modifier;

the modifier is selected from an acrylic acid modifier or an acrylate modifier;

the two-dimensional nano material is selected from any one or the combination of at least two of nano zirconium phosphate, modified graphene, montmorillonite, talcum powder or titanium dioxide nanosheets;

the modified graphene is graphene oxide;

d of the two-dimensional nanomaterial ₉₀ The particle size is 30 to 5000 nm;

the raw materials for preparing the modified two-dimensional nano material also comprise 0.5 to 2 parts of silane coupling agent;

the preparation method of the modified two-dimensional nano material is selected from the method A or the method B;

the method A comprises the following steps:

uniformly mixing a two-dimensional nano material and a solvent, adding an acrylic acid modifier and a catalyst, and carrying out modification reaction to obtain a modified two-dimensional nano material;

the method B comprises the following steps:

(2) Adding an acrylate modifier and a catalyst into the mixture A obtained in the step (1) for modification reaction to obtain the modified two-dimensional nano material;

the catalyst is selected from any one or a combination of at least two of concentrated sulfuric acid, p-toluenesulfonic acid, tetrabutyltin or methanesulfonic acid;

(B) And (B) uniformly mixing the mixture obtained in the step (A) with a UV resin oligomer, an acrylic monomer, a photoinitiator and an optional organic solvent to obtain the UV-cured super-hydrophilic antifogging coating.

2. The UV-curable superhydrophilic repellent of claim 1Mist coating, characterized in that D of the two-dimensional nanomaterial ₉₀ The particle size is 50 to 2000nm.

3. The UV-curable superhydrophilic antifogging coating of claim 1, wherein said acrylic modifier is selected from any one or a combination of at least two of acrylic acid, phenylacrylic acid, imidazoleacrylic acid, pyridylacrylic acid, paraphenylenediacrylic acid, ethoxybenzoylacrylic acid, acetamidoacrylic acid, thiopheneacrylic acid, or furanpropenoic acid.

4. The UV-curable superhydrophilic antifog coating of claim 1, wherein said acrylate modifier is selected from any one or a combination of at least two of methyl methacrylate, ethyl methacrylate, butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, isobutyl acrylate or t-butyl acrylate.

5. The UV-curable super-hydrophilic antifogging coating of claim 1, wherein the weight part of the catalyst in the raw materials for preparing the modified two-dimensional nanomaterial is 0.01 to 0.1.

6. The UV-curable super-hydrophilic antifogging coating of claim 1, wherein the solvent in the raw materials for preparing the modified two-dimensional nanomaterial is 20 to 30 parts by weight.

7. The UV-curable superhydrophilic antifogging coating of claim 1, wherein said solvent is selected from any one or a combination of at least two of deionized water, ethanol, isopropanol or toluene.

8. The UV-curable superhydrophilic antifogging coating of claim 1, wherein said silane coupling agent is selected from any one of or a combination of at least two of vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris (methoxyethoxy) silane, methacryloxypropyltriethoxysilane, 3- (methacryloxy) propyltrimethoxysilane or 3-methacryloxypropylmethyldimethoxysilane.

9. The UV-curable super-hydrophilic antifogging coating of claim 1, wherein the temperature of the modification reaction of method A is 70 to 90 ℃.

10. The UV-curable super-hydrophilic antifogging coating of claim 1, wherein the modification reaction time of method A is 3 to 8 hours.

11. The UV-curable superhydrophilic antifogging coating of claim 1, further comprising a step of post-treatment after completion of said modification reaction of method A.

12. The UV-curable super-hydrophilic antifogging coating according to claim 11, wherein the post-treatment method is suction filtration, cleaning and drying.

13. The UV-curable super-hydrophilic antifogging coating of claim 1, wherein the reaction temperature in step (1) is 50-80 ℃.

14. The UV-curable super-hydrophilic antifogging coating of claim 1, wherein the reaction time in step (1) is 0.5 to 3 hours.

15. The UV-curable super-hydrophilic antifogging coating of claim 1, wherein the temperature of the reaction in step (2) is 50-80 ℃.

16. The UV-cured super-hydrophilic antifogging coating of claim 1, wherein the time of the modification reaction in the step (2) is 1 to 5 hours.

17. The UV-curable superhydrophilic antifogging coating of claim 1, further comprising a step of post-treatment after the modification reaction of step (2) is completed.

18. The UV-curable super-hydrophilic antifogging coating of claim 17, wherein the post-treatment method is suction filtration, cleaning and drying.

19. The UV-curable super-hydrophilic antifogging coating of claim 1, wherein the number average molecular weight of the UV resin oligomer is 1000 to 3000.

20. The UV-curable superhydrophilic antifog coating of claim 1, wherein said acrylic monomer is selected from any one of acrylic acid, methyl methacrylate, ethyl methacrylate, butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, isobornyl methacrylate, dicyclopentadiene acrylate, trimethylol cyclohexyl acrylate, hydroxybutyl acrylate or phenoxyethyl acrylate or a combination of at least two thereof.

21. The UV-curable super-hydrophilic antifogging coating of claim 1, wherein the surfactant is selected from any one or a combination of at least two of polyether modified polydimethylsiloxane, polyester modified polydimethylsiloxane, perfluoroalkyl polyoxyethylene ether, long-chain fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene ether, fatty acid polyoxyethylene ester, polyoxyethylene alkylamine, or polyoxyethylene alkylolamide.

22. The UV-curable super-hydrophilic antifogging coating of claim 1, further comprising 2 to 6 parts of photoinitiator.

23. The UV-curable superhydrophilic antifog coating of claim 22, wherein said photoinitiator is selected from any one or a combination of at least two of photoinitiator 1173, photoinitiator 184, photoinitiator TPO-L or photoinitiator 819.

24. A method for preparing the UV-curable superhydrophilic anti-fog coating of any one of claims 1-23, wherein the method for preparing comprises the steps of:

25. The method according to claim 24, wherein the temperature for mixing in step (A) is 50 to 80 ℃.

26. The method of claim 24, wherein the mixing in step (A) is performed for a time period of 1h or more.

27. Use of the UV-curable superhydrophilic anti-fog coating of any one of claims 1-23 in an anti-fog coating or film.