阅读说明：本技术 一种长效耐磨的纳米防雾剂及其制备方法和应用 (Long-acting wear-resistant nano antifogging agent and preparation method and application thereof ) 是由 钟明伟 周平乐 于 2021-08-01 设计创作，主要内容包括：本发明公开了一种长效耐磨的纳米防雾剂及其制备方法和应用,其方法有以下步骤,先将碱金属氢氧化物与乙醇溶液超声混合完全得到透明溶液,加入醋酸盐进行常温搅拌制备胶体溶液,再加入四乙氧基硅烷,减压蒸出乙醇得到纳米粒子。使用时,将纳米粒子溶于加有成膜剂和偶联剂的混合溶剂中进行涂膜,即可实现耐磨防雾效果。本发明的纳米防雾剂制备方法简单,制备时间短,常温反应,且环保、无毒,可用于PET、PP等塑料材质的防护眼镜、防护面罩的防雾耐磨处理。(The invention discloses a long-acting wear-resistant nano antifogging agent and a preparation method and application thereof. When in use, the nano particles are dissolved in the mixed solvent with the film forming agent and the coupling agent for film coating, thus realizing the wear-resistant anti-fog effect. The nano antifogging agent disclosed by the invention is simple in preparation method, short in preparation time, capable of reacting at normal temperature, environment-friendly and nontoxic, and can be used for antifogging and wear-resistant treatment of protective glasses and protective masks made of plastic materials such as PET (polyethylene terephthalate) and PP (polypropylene).)

1. A preparation method of a long-acting wear-resistant nano antifogging agent is characterized by comprising the following steps: firstly, completely mixing alkali metal hydroxide and ethanol solution by ultrasonic to obtain transparent solution, wherein the alkali metal hydroxide is one of sodium hydroxide and potassium hydroxide;

then, adding acetate with the molar ratio of the alkali metal oxide to the acetate of 1:1-4:1 into the transparent solution, stirring at 25-35 ℃ to prepare a colloidal solution containing the nano metal oxide, wherein the acetate is one of zinc acetate and copper acetate, and the particle size of the nano metal oxide is not more than 50 nm;

adding tetraethoxysilane into the colloidal solution containing the nano metal oxide according to the molar ratio of tetraethoxysilane to acetate of 1:1-4:1, stirring for 0.5-3h at the temperature of 25-35 ℃ to prepare colloidal mixed liquid containing the nano metal oxide coated by the nano silicon dioxide, dropwise adding acetic acid to adjust the pH of the colloidal mixed liquid to be 5.5-6.5, uniformly stirring, and finally decompressing and evaporating ethanol to obtain the core-shell nano particle of the nano metal oxide coated by the nano silicon dioxide shell.

2. The preparation method of the long-acting wear-resistant nano antifogging agent according to claim 1, characterized in that: the range of the particle size of the nano metal oxide is as follows: 1-20 nm.

3. The preparation method of the long-acting wear-resistant nano antifogging agent according to claim 1, characterized in that: the particle size of the nano-silica coated nano-metal oxide nanoparticles is 10-30nm, the diameter of the core of the nanoparticles is 1-10nm, and the thickness of the shell of the nanoparticles is 2-12 nm.

4. The preparation method of the long-acting wear-resistant nano antifogging agent according to claim 1, characterized in that: the film forming agent is at least one of acrylic resin, polyvinyl pyrrolidone and sodium di (2-ethylhexyl) succinate sulfonate.

5. The preparation method of the long-acting wear-resistant nano antifogging agent according to claim 1, characterized in that: the coupling agent is 3- (trimethoxysilyl) propyl methacrylate.

6. The preparation method of the long-acting wear-resistant nano antifogging agent according to claim 1, characterized in that: the mixed solvent is at least one of ethanol, isopropanol and water.

7. A long-acting wear-resistant nano antifogging agent is characterized in that: the nano-particle comprises a core and a nano-silica shell coated on the surface of the core, wherein the core is one of zinc oxide or copper oxide, the diameter of the core is 1-10nm, and the thickness of the nano-silica shell is 2-12 nm.

8. The long-acting wear-resistant nano antifogging agent according to claim 7, characterized in that: the coating also comprises a film forming agent, a coupling agent and a mixed solvent capable of dissolving the film forming agent and the coupling agent at the same time, wherein the ratio of the film forming agent to the coupling agent is (5: 1) - (21): 1.

9. the long-acting wear-resistant nano antifogging agent according to claim 8, wherein the film forming agent is at least one of acrylic resin, polyvinylpyrrolidone and sodium di (2-ethylhexyl) sulfosuccinate, preferably acrylic resin; the coupling agent is 3- (trimethoxysilyl) propyl methacrylate.

10. Use of the nano antifogging agent prepared by the method of claim 1 or the nano antifogging agent of claim 7 for preparing an antifogging coating on the surface of an optical lens, characterized in that: the thickness of the antifogging coating is 5nm-500 um.

Technical Field

The invention belongs to the technical field of lens surface modification, and particularly relates to a long-acting wear-resistant nano antifogging agent as well as a preparation method and application thereof.

Background

The optical lens has different applications in the fields of people's life, medical treatment and health, industrial and mining industry, scientific research and the like, such as glasses, medical goggles, gas masks, automobile windows and rearview mirrors, endoscopes, cameras and the like which are worn by people in daily life. In the using process of the lens, the surface of the lens is easy to scratch and generate lines, so that the service life of the lens is influenced; when the lens is used in rainy and snowy weather, winter or in an environment with heavy water vapor, the lens is easily covered by fog, so that the visual field is blurred.

In order to overcome the above disadvantages, there are several solutions, which can adopt a mechanical structure such as a wiper to solve the fog problem, or adopt an antifogging agent spraying manner, but more than spray a hydrophilic polymer antifogging agent on the surface of the lens to achieve the purpose, but the hydrophilic polymer antifogging agent has the defects of low hardness, no wear resistance, easy erosion, short service life, etc.

Disclosure of Invention

In order to overcome the defects of the prior art, the invention provides a preparation method of a long-acting wear-resistant nano antifogging agent, which has simple reaction conditions and low cost.

In order to achieve the purpose, the invention adopts the technical scheme that: a preparation method of a long-acting wear-resistant nano antifogging agent is characterized by comprising the following steps: firstly, completely mixing alkali metal hydroxide and ethanol solution by ultrasonic to obtain transparent solution, wherein the alkali metal hydroxide is one of sodium hydroxide and potassium hydroxide;

then, adding acetate with the molar ratio of the alkali metal oxide to the acetate of 1:1-4:1 into the transparent solution, stirring at 25-35 ℃ to prepare a colloidal solution containing the nano metal oxide, wherein the acetate is one of zinc acetate and copper acetate, and the particle size of the nano metal oxide is not more than 50 nm;

adding tetraethoxysilane into a colloidal solution containing nano metal oxide according to the molar ratio of tetraethoxysilane to acetate of 1:1-4:1, stirring for 0.5-3h at 25-35 ℃ to prepare a colloidal mixed solution containing nano silicon dioxide coated nano metal oxide, dropwise adding acetic acid to adjust the pH of the colloidal mixed solution to 5.5-6.5, uniformly stirring, and finally decompressing and evaporating ethanol to obtain the core-shell nano metal oxide nano particles coated with the nano silicon dioxide shell.

Further, the range of the particle diameter d of the nano metal oxide is as follows: 1. ltoreq. d.ltoreq.20 nm, the particle size d may preferably be from 1 to 10, and also preferably from 10 to 20nm, for example 1nm < d < 10nm or 10nm < d < 20nm or d 20 nm.

Furthermore, the particle diameter of the nano-silica coated nano-metal oxide nano-particle is 10-30nm, the diameter of the middle core of the nano-particle is 1-10nm, and the thickness of the outer shell of the nano-particle is 2-12 nm.

Furthermore, the film forming agent is at least one of acrylic resin, polyvinyl pyrrolidone and sodium di (2-ethylhexyl) succinate sulfonate.

Further, the coupling agent is 3- (trimethoxysilyl) propyl methacrylate.

Further, the mixed solvent of the film forming agent is at least one of ethanol, isopropanol and water.

By adopting the scheme, the nano antifogging agent disclosed by the invention is simple in preparation method, short in preparation time, capable of reacting at normal temperature, environment-friendly and nontoxic, and can be used for antifogging and wear-resistant treatment of protective glasses and protective masks made of plastic materials such as PET (polyethylene terephthalate) and PP (polypropylene).

Another object of the invention is: the invention also provides a long-acting wear-resistant nano antifogging agent, which is characterized in that: the nano-particle comprises a core and a nano-silica shell coated on the surface of the core, wherein the core is one of zinc oxide or copper oxide, the diameter of the core is 1-10nm, and the thickness of the nano-silica shell is 2-12 nm.

Further, the coating comprises a film forming agent, a coupling agent and a mixed solvent capable of dissolving the film forming agent and the coupling agent simultaneously, wherein the ratio of the film forming agent to the coupling agent is (5: 1) - (21): 1. further, the mixed solvent is at least one of ethanol, isopropanol and water.

Further, the film forming agent is at least one of acrylic resin, polyvinylpyrrolidone and sodium bis (2-ethylhexyl) succinate, and the coupling agent is 3- (trimethoxysilyl) propyl methacrylate.

Another object of the invention is: the invention also provides a nano antifogging agent prepared by the method or an application of the nano antifogging agent in preparing an antifogging coating on the surface of an optical lens, which is characterized in that: the thickness of the antifogging coating is 5nm-500 um. Preferably, 20nm to 200 um.

By adopting the scheme, the coating prepared from the nano antifogging agent has the following advantages:

1) the wear resistance of the material is improved, so that the hardness of the material is increased and the service life of the material is prolonged;

2) the antifogging performance of the transparent material is improved;

3) the preparation method is simple and can be realized at normal temperature.

The invention is further described below with reference to the accompanying drawings.

Drawings

FIG. 1 is a TEM of a sample of an embodiment 4 of the present invention.

Detailed Description

Firstly, completely mixing alkali metal hydroxide and ethanol solution by ultrasonic to obtain transparent solution, then adding acetate into the transparent solution, stirring at 25-35 ℃ to prepare colloidal solution containing nano metal oxide, then adding tetraethoxysilane into the colloidal solution containing nano metal oxide, stirring at 25-35 ℃ for 0.5-3h to prepare colloidal mixed solution containing nano silicon dioxide coated nano metal oxide, dropwise adding acetic acid to adjust the pH of the colloidal mixed solution to be 5.5-6.5, stirring uniformly, and finally evaporating ethanol under reduced pressure to obtain the nano silicon dioxide shell coated nano metal oxide core-shell nano particles. When in use, 3.8g of the nanoparticles are added into a mixture containing acrylic resin and 3- (trimethoxysilyl) propyl methacrylate in a mass ratio of 5: 1-21: 1, stirring for 1h to obtain the nano wear-resistant antifogging agent, wherein the mass ratio of ethanol to water is 20:1, and the nano wear-resistant antifogging agent is coated to form a coating thickness of 5nm-500 mu m, so that the nano wear-resistant antifogging agent has a relatively good antifogging and wear-resistant effect.

In this example, a nano wear-resistant antifogging agent was coated on a 0.5mm thick PET sheet by an applicator, dried at 70 ℃ and placed on a 80 ℃ thermostatic water bath cup, and the antifogging effect was observed by visual observation at different times (see Table 2). The thickness of the antifogging coating formed after the antifogging agent is dried can be within 5nm-500um, if the thickness of the coating is more than 500um, the light transmittance can be reduced, if the thickness of the coating is less than the range, the antifogging effect cannot be achieved, the wear resistance is poor, but preferably, the thickness of the coating is within 20nm-200um, and the antifogging wear-resistant effect and the definition can be very good. In the embodiment, the antifogging effect and the wear resistance of the nano wear-resistant antifogging coating with the thickness of 55nm formed by coating are tested by taking the example as an example.

A nano wear-resistant antifogging coating is coated on a PET plastic sheet, and the scratch resistance is evaluated by a pencil hardness method (see table 3).

The specific example proportions are shown in the following table:

TABLE 1 Material proportioning Table in different examples

TABLE 2 antifogging effect after different times

Note: OK means no visible haze development on the PET sheet and Fail means visible haze development on the naked eye. As shown in FIG. 1, example 4 has a nanoparticle size of about 15nm, a core diameter of about 3nm and a shell thickness of about 6 nm.

TABLE 3 Pencil hardness method for testing wear resistance of samples

The present invention is not limited to the above embodiments, and those skilled in the art can implement the present invention in other embodiments according to the disclosure of the present invention, or make simple changes or modifications on the design structure and idea of the present invention, and fall into the protection scope of the present invention.