Anti-static high-hardness coating and preparation process thereof

Abstract

The invention relates to the technical field of coatings, in particular to an antistatic high-hardness coating and a preparation process thereof. Specifically, the coating is composed of a component A and a component B. The component A is prepared from, by weight, 80-100 parts of water-borne epoxy resin emulsion, 1-2 parts of dispersing agent, 1-2 parts of KH550 and 5-30 parts of cyclodextrin modified g-C3N4 / ATO composite nanomaterial. And the component B comprises the following components in parts by weight: 20-50 parts of a water-based curing agent and 1-3 parts of a curing accelerator. The cyclodextrin-modified g-C3N4 has good chemical stability and adsorbability, and after the cyclodextrin-modified g-C3N4 is combined with ATO nanoparticles, the coating is endowed with antistatic performance, and the hardness and adhesive force of the coating are also possibly improved. The preparation process is simple, the production efficiency is high, and large-scale production can be quickly realized. By adjusting the ratio of the component A to the component B, the performance of the coating can be flexibly controlled, and the requirements of different application scenes can be met. The coating has good anti-static performance and can be used in the fields of airplanes, high-speed rails and the like.

Description

Technical Field

[0001] The present invention relates to the technical field of coatings, in particular to an antistatic high-hardness coating and a preparation process thereof. Background Art

[0002] With the development of the country and the advancement of science and technology, people's functional demands for materials are becoming increasingly diversified. As a functional material, the market demand for coatings is also growing. Conductive coatings have attracted particular attention due to their special properties. They are widely used in electronics, construction, automobiles, aerospace and other fields. For example, they are used for electromagnetic shielding and heat dissipation coatings in electronic equipment, for lightning protection grounding and electromagnetic shielding in the construction field, for body painting and anti-static in the car in automobiles, and for improving the surface performance of high-temperature wear-resistant parts in aerospace. Conductive coatings can be divided into metal conductive coatings, carbon conductive coatings and metal oxide conductive coatings according to the different conductive fillers, which are suitable for different application scenarios. In the future, conductive coatings will develop in the direction of high performance, environmental protection and multifunctionality to meet the growing market demand.

[0003] Antimony tin oxide (ATO) can be used as an antistatic additive. It is an excellent conductive material with excellent conductivity, transparency, and chemical stability. In antistatic coatings, ATO effectively dissipates static charges and prevents static buildup. Furthermore, it is highly transparent and has minimal absorption of visible light, which does not affect the transparency of the coating. Therefore, ATO is widely used in coatings, plastics, textiles, and other fields to enhance the antistatic properties of materials.

[0004] In the existing technology, "A novel core-shell silica@graphene straticulate structured antistatic anticorrosion composite coating" combines ATO, reduced graphene oxide and functionalized silica to improve the anti-corrosion and antistatic properties of the coating, but there is little research on improving the hardness and other properties of the coating. Summary of the Invention

[0005] In order to solve the problems existing in the prior art, the present invention provides an antistatic high-hardness coating and a preparation process thereof.

[0006] The present invention is achieved through the following technical solutions:

[0007] An antistatic high-hardness coating, composed of component A and component B, wherein component A comprises, by weight: 80-100 parts of waterborne epoxy resin emulsion, 1-2 parts of dispersant, 1-2 parts of KH550, and 5-30 parts of cyclodextrin-modified g-C3N4 / ATO composite nanomaterial;

[0008] Component B comprises, by weight: 20 to 50 parts of a water-based curing agent and 1 to 3 parts of a curing accelerator.

[0009] Furthermore, the dispersant in component A is selected from one of sodium lauryl sulfate, sodium tripolyphosphate, and sodium secondary alkyl sulfonate.

[0010] Furthermore, the water-based curing agent in the B component is selected from phenolic modified fatty amine epoxy curing agent.

[0011] Furthermore, the water-based curing agent in the B component is selected from T31.

[0012] Furthermore, the curing accelerator is one of isophorone diamine and 2-ethyl-4-methylimidazole.

[0013] Furthermore, the curing accelerator is isophoronediamine.

[0014] Furthermore, the preparation method of the cyclodextrin modified g-C3N4 / ATO composite nanomaterial is:

[0015] ATO nanoparticles and cyclodextrin-modified g-C3N4 nanocomposites were mixed in a mass ratio of 1:1 and then immersed in 50 mL of ethanol and ultrasonicated for 2 hours; the mixed solution was then dried at 90 degrees Celsius for 24 hours and then heat-treated at 150 degrees Celsius for 3 hours. After cooling, cyclodextrin-modified g-C3N4 / ATO composite nanomaterials were obtained.

[0016] Furthermore, the preparation method of the ATO nanoparticles is as follows: 18.54 mmol SnCl4, 2.5 mmol SbCl3, 12 g ammonium bicarbonate and 4 g acetic acid are added to 100 mL of anhydrous ethanol, 25% wt% NH4OH is used to adjust the pH to 7, stirred for 4 hours, and then centrifuged to obtain a precipitate, the precipitate is washed 3 times with deionized water, and then the precipitate is heated at 550 degrees Celsius in a muffle furnace for 8 hours, and naturally cooled to obtain ATO nanoparticles.

[0017] Furthermore, the preparation method of the cyclodextrin-modified g-C3N4 nanocomposite is as follows: 4 g of cyclodextrin is added to 50 mL of DMF, and then 0.75 g of KH560 is added and stirred for 6 hours; then 2 g of g-C3N4 is added and stirred for 12 hours, centrifuged to obtain a precipitate, and the precipitate is washed with ethanol and deionized water respectively, and then dried at 80 degrees Celsius for 12 hours to obtain a cyclodextrin-modified g-C3N4 nanocomposite.

[0018] The present invention also provides a preparation process of an antistatic high-hardness coating, comprising the following steps: fully mixing component A and component B, stirring, and then ultrasonically dispersing to obtain the antistatic high-hardness coating.

[0019] Compared with the prior art, the present invention has the following advantages and beneficial effects:

[0020] The cyclodextrin-modified g-C3N4 in this invention exhibits excellent chemical stability and adsorption properties. When combined with ATO nanoparticles, it not only imparts antistatic properties to the coating but also potentially improves its hardness and adhesion. The preparation process is simple, with high production efficiency, enabling rapid large-scale production. By adjusting the ratio of components A and B, the coating's properties can be flexibly controlled to meet the needs of diverse application scenarios. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] The drawings described herein are used to provide a further understanding of the embodiments of the present invention, constitute a part of this application, and do not constitute a limitation of the embodiments of the present invention.

[0022] Figure 1 TEM image of cyclodextrin modified g-C3N4 / ATO composite nanomaterial in the present invention; DETAILED DESCRIPTION

[0023] In order to make the objectives, technical solutions and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with examples and drawings. The exemplary embodiments of the present invention and their descriptions are only used to explain the present invention and are not intended to limit the present invention.

[0024] The preparation method of ATO nanoparticles in the present invention:

[0025] 18.54 mmol SnCl4, 2.5 mmol SbCl3, 12 g ammonium bicarbonate and 4 g acetic acid were added to 100 mL of anhydrous ethanol, the pH was adjusted to 7 with 25% wt% NH4OH, stirred for 4 h, and then centrifuged to obtain a precipitate. The precipitate was washed three times with deionized water, and then the precipitate was heated at 550 degrees Celsius in a muffle furnace for 8 h. After natural cooling, ATO nanoparticles were obtained.

[0026] The preparation method of g-C3N4 in the present invention is:

[0027] Melamine was heated at 550 °C in a muffle furnace for 3 h. After natural cooling, the obtained powder was ground into fine powder and heated at 550 °C for 3 h again. The precipitate was then washed with 0.1 M nitric acid and deionized water, respectively, and then dried at 80 °C for 6 h to obtain g-C3N4.

[0028] Preparation of g-C3N4 / ATO composite nanomaterials in the present invention:

[0029] ATO nanoparticles and g-C3N4 were mixed in a mass ratio of 1:1 and then immersed in 50 mL of ethanol and ultrasonicated for 2 hours; the mixed solution was then dried at 90 degrees Celsius for 24 hours and then heat treated at 150 degrees Celsius for 3 hours. After cooling, g-C3N4 / ATO composite nanomaterials were obtained.

[0030] Preparation of cyclodextrin-modified g-C3N4 nanocomposite in the present invention:

[0031] 4 g of cyclodextrin was added to 50 mL of DMF, followed by 0.75 g of KH560 and stirring for 6 h. 2 g of g-C3N4 was then added and stirred for 12 h. The mixture was centrifuged to obtain a precipitate, which was washed with ethanol and deionized water, respectively, and then dried at 80 degrees Celsius for 12 h to obtain a cyclodextrin-modified g-C3N4 nanocomposite.

[0032] Preparation of cyclodextrin modified g-C3N4 / ATO composite nanomaterials in the present invention:

[0033] ATO nanoparticles and cyclodextrin-modified g-C3N4 nanocomposites were mixed in a mass ratio of 1:1 and then immersed in 50 mL of ethanol and ultrasonicated for 2 h. The mixed solution was then dried at 90 degrees Celsius for 24 h and then heat-treated at 150 degrees Celsius for 3 h. After cooling, cyclodextrin-modified g-C3N4 / ATO composite nanomaterials were obtained. Figure 1 TEM image of cyclodextrin modified g-C3N4 / ATO composite nanomaterials.

[0034] Example 1: An antistatic high-hardness coating

[0035] An antistatic high-hardness coating, component A: 100 parts of water-based epoxy resin emulsion, 1 part of dispersant sodium dodecylsulfonate, 2 parts of KH550, and 5 parts of cyclodextrin-modified g-C3N4 / ATO composite nanomaterial;

[0036] Component B: 40 parts of water-based curing agent T31, 1 part of isophorone diamine;

[0037] A method for preparing an antistatic high-hardness coating comprises adding a cyclodextrin-modified g-C3N4 / ATO composite nanomaterial to a water-based epoxy resin emulsion, stirring for 5 minutes, then adding KH550 and a dispersant, sodium dodecylsulfonate, and stirring for 5 minutes to obtain component A;

[0038] Mix water-based curing agent T31 and isophorone diamine and stir for 5 minutes to obtain component B;

[0039] Component A and component B were fully mixed, stirred for 20 minutes, and then ultrasonically dispersed for 10 minutes to obtain an antistatic high-hardness coating.

[0040] Example 2

[0041] An antistatic high-hardness coating, component A: 100 parts of water-based epoxy resin emulsion, 1 part of dispersant sodium dodecylsulfonate, 2 parts of KH550, and 10 parts of cyclodextrin-modified g-C3N4 / A1TO composite nanomaterial;

[0042] Component B: 40 parts of water-based curing agent T31, 1 part of isophorone diamine;

[0043] A method for preparing an antistatic high-hardness coating comprises adding a cyclodextrin-modified g-C3N4 / ATO composite nanomaterial to a water-based epoxy resin emulsion, stirring for 5 minutes, then adding KH550 and a dispersant, sodium dodecylsulfonate, and stirring for 5 minutes to obtain component A;

[0044] Mix water-based curing agent T31 and isophorone diamine and stir for 5 minutes to obtain component B;

[0045] Component A and component B were fully mixed, stirred for 20 minutes, and then ultrasonically dispersed for 10 minutes to obtain an antistatic high-hardness coating.

[0046] Example 3

[0047] An antistatic high-hardness coating, component A: 100 parts of water-based epoxy resin emulsion, 1 part of dispersant sodium dodecylsulfonate, 2 parts of KH550, and 15 parts of cyclodextrin-modified g-C3N4 / ATO composite nanomaterial;

[0048] Component B: 40 parts of water-based curing agent T31, 1 part of isophorone diamine;

[0049] A method for preparing an antistatic high-hardness coating comprises adding a cyclodextrin-modified g-C3N4 / ATO composite nanomaterial to a water-based epoxy resin emulsion, stirring for 5 minutes, then adding KH550 and a dispersant, sodium dodecylsulfonate, and stirring for 5 minutes to obtain component A;

[0050] Mix water-based curing agent T31 and isophorone diamine and stir for 5 minutes to obtain component B;

[0051] Component A and component B were fully mixed, stirred for 20 minutes, and then ultrasonically dispersed for 10 minutes to obtain an antistatic high-hardness coating.

[0052] Example 4

[0053] An antistatic high-hardness coating, component A: 100 parts of water-based epoxy resin emulsion, 1 part of dispersant sodium dodecylsulfonate, 2 parts of KH550, and 20 parts of cyclodextrin-modified g-C3N4 / ATO composite nanomaterial;

[0054] Component B: 40 parts of water-based curing agent T31, 1 part of isophorone diamine;

[0055] A method for preparing an antistatic high-hardness coating comprises adding a cyclodextrin-modified g-C3N4 / ATO composite nanomaterial to a water-based epoxy resin emulsion, stirring for 5 minutes, then adding KH550 and a dispersant, sodium dodecylsulfonate, and stirring for 5 minutes to obtain component A;

[0056] Mix water-based curing agent T31 and isophorone diamine and stir for 5 minutes to obtain component B;

[0057] Component A and component B were fully mixed, stirred for 20 minutes, and then ultrasonically dispersed for 10 minutes to obtain an antistatic high-hardness coating.

[0058] Example 5

[0059] An antistatic high-hardness coating, component A: 100 parts of water-based epoxy resin emulsion, 1 part of dispersant sodium dodecylsulfonate, 2 parts of KH550, and 25 parts of cyclodextrin-modified g-C3N4 / ATO composite nanomaterial;

[0060] Component B: 40 parts of water-based curing agent T31, 1 part of isophorone diamine;

[0061] A method for preparing an antistatic high-hardness coating comprises adding a cyclodextrin-modified g-C3N4 / ATO composite nanomaterial to a water-based epoxy resin emulsion, stirring for 5 minutes, then adding KH550 and a dispersant, sodium dodecylsulfonate, and stirring for 5 minutes to obtain component A;

[0062] Mix water-based curing agent T31 and isophorone diamine and stir for 5 minutes to obtain component B;

[0063] Component A and component B were fully mixed, stirred for 20 minutes, and then ultrasonically dispersed for 10 minutes to obtain an antistatic high-hardness coating.

[0064] Example 6

[0065] An antistatic high-hardness coating, component A: 100 parts of water-based epoxy resin emulsion, 1 part of dispersant sodium dodecylsulfonate, 2 parts of KH550, and 30 parts of cyclodextrin-modified g-C3N4 / ATO composite nanomaterial;

[0066] Component B: 40 parts of water-based curing agent T31, 1 part of isophorone diamine;

[0067] A method for preparing an antistatic high-hardness coating comprises adding a cyclodextrin-modified g-C3N4 / ATO composite nanomaterial to a water-based epoxy resin emulsion, stirring for 5 minutes, then adding KH550 and a dispersant, sodium dodecylsulfonate, and stirring for 5 minutes to obtain component A;

[0068] Mix water-based curing agent T31 and isophorone diamine and stir for 5 minutes to obtain component B;

[0069] Component A and component B were fully mixed, stirred for 20 minutes, and then ultrasonically dispersed for 10 minutes to obtain an antistatic high-hardness coating.

[0070] Comparative Example 1

[0071] An antistatic high-hardness coating, component A: 100 parts of water-based epoxy resin emulsion, 1 part of dispersant sodium dodecylsulfonate, 2 parts of KH550, and 20 parts of g-C3N4 / ATO composite nanomaterial;

[0072] Component B: 40 parts of water-based curing agent T31, 1 part of isophorone diamine;

[0073] A method for preparing an antistatic high-hardness coating comprises adding g-C3N4 / ATO composite nanomaterial to a water-based epoxy resin emulsion, stirring for 5 minutes, then adding KH550 and dispersant sodium dodecylsulfonate, stirring for 5 minutes, and obtaining component A.

[0074] Mix water-based curing agent T31 and isophorone diamine and stir for 5 minutes to obtain component B;

[0075] Component A and component B were fully mixed, stirred for 20 minutes, and then ultrasonically dispersed for 10 minutes to obtain an antistatic high-hardness coating.

[0076] Comparative Example 2

[0077] An antistatic high-hardness coating, component A: 100 parts of water-based epoxy resin emulsion, 1 part of dispersant sodium dodecylsulfonate, 2 parts of KH550, and 20 parts of ATO nanomaterial;

[0078] Component B: 40 parts of water-based curing agent T31, 1 part of isophorone diamine;

[0079] A method for preparing an antistatic high-hardness coating comprises: adding ATO nanomaterial to a water-based epoxy resin emulsion, stirring for 5 minutes, then adding KH550 and dispersant sodium dodecylsulfonate, stirring for 5 minutes, and obtaining component A;

[0080] Mix water-based curing agent T31 and isophorone diamine and stir for 5 minutes to obtain component B;

[0081] Component A and component B were fully mixed, stirred for 20 minutes, and then ultrasonically dispersed for 10 minutes to obtain an antistatic high-hardness coating.

[0082] Test Example 1

[0083] The tinplate sheets were polished with 600-1000# sandpaper in sequence, ultrasonically cleaned with acetone and deionized water respectively, and dried for use. The coatings prepared in each embodiment and comparative example were evenly coated on the treated tinplate sheets to a coating thickness of about 100 μm. After coating, the test pieces were placed in an oven at 40 degrees Celsius and dried for 10 hours to obtain the product.

[0084] The hardness of the coating was tested using Shore A hardness tester. The adhesion of the coating was tested according to GB / T 1720 paint film adhesion. The surface resistance was tested using a hammer-type surface resistance tester.

[0085] Table 1 Performance test

[0086] Hardness / Shore A Adhesion / Grade <![CDATA[Surface resistance (Ω, × 10 10 )]]> Example 1 90.1 2 60.2 Example 2 92.3 1-2 35.3 Example 3 93.4 0 20.4 Example 4 94.4 0 15.8 Example 5 94.7 0 10.2 Example 6 94.2 0 4.5 Comparative Example 1 84.7 1-2 15.2 Comparative Example 2 84.2 1-2 10.3

[0087] As can be seen from Table 1, the addition of cyclodextrin-modified g-C3N4 / ATO composite nanomaterials to the coating has better hardness than g-C3N4 / ATO composite nanomaterials and ATO alone at the same content. The cyclodextrin-modified g-C3N4 / ATO composite nanomaterials can better adsorb into the network structure formed by the epoxy resin, playing a certain supporting role. The cyclodextrin-modified g-C3N4 / ATO composite nanomaterials themselves are also more easily evenly dispersed in the coating, improving the hardness of the coating. In the coating, ATO is better dispersed in the coating in the form of cyclodextrin-modified g-C3N4 / ATO composite nanomaterials, improving the conductive properties.

[0088] The specific implementation methods described above further illustrate the objectives, technical solutions and beneficial effects of the present invention in detail. It should be understood that the above description is only a specific implementation method of the present invention and is not intended to limit the scope of protection of the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.

Claims

1. An antistatic high hardness coating, characterized in that: The method is composed of component A and component B, wherein component A comprises, by weight: 80-100 parts of waterborne epoxy resin emulsion, 1-2 parts of dispersant, 1-2 parts of KH550, and 5-30 parts of cyclodextrin-modified g-C3N4 / ATO composite nanomaterial; Component B comprises, by weight: 20 to 50 parts of a water-based curing agent and 1 to 3 parts of a curing accelerator.

2. The antistatic high hardness coating according to claim 1, characterized in that: The dispersant in the component A is selected from one of sodium lauryl sulfate, sodium tripolyphosphate and sodium secondary alkyl sulfonate.

3. The antistatic high hardness coating according to claim 1, characterized in that: The water-based curing agent in the B component is selected from phenolic modified fatty amine epoxy curing agent.

4. The antistatic high hardness coating according to claim 3, characterized in that: The water-based curing agent in the B component is selected from T31.

5. The antistatic high hardness coating according to claim 4, characterized in that: The curing accelerator is one of isophorone diamine and 2-ethyl-4-methylimidazole.

6. The antistatic high hardness coating according to claim 4, characterized in that: The curing accelerator is isophorone diamine.

7. The antistatic high hardness coating according to claim 1, characterized in that: The preparation method of the cyclodextrin modified g-C3N4 / ATO composite nanomaterial is as follows: ATO nanoparticles and cyclodextrin-modified g-C3N4 nanocomposites were mixed in a mass ratio of 1:1 and then immersed in 50 mL of ethanol and ultrasonicated for 2 hours; the mixed solution was then dried at 90 degrees Celsius for 24 hours and then heat-treated at 150 degrees Celsius for 3 hours. After cooling, cyclodextrin-modified g-C3N4 / ATO composite nanomaterials were obtained.

8. The antistatic high-hardness coating according to claim 7, characterized in that: The preparation method of the ATO nanoparticles is as follows: 18.54 mmol SnCl4, 2.5 mmol SbCl3, 12 g ammonium bicarbonate and 4 g acetic acid are added to 100 mL of anhydrous ethanol, the pH is adjusted to 7 with 25% wt% NH4OH, stirred for 4 hours, and then centrifuged to obtain a precipitate, the precipitate is washed three times with deionized water, and then the precipitate is heated at 550 degrees Celsius in a muffle furnace for 8 hours. After natural cooling, ATO nanoparticles are obtained.

9. A process for preparing the antistatic high-hardness coating according to any one of claims 1 to 8, characterized in that: The following steps are involved: The components A and B are fully mixed, stirred, and then ultrasonically dispersed to obtain an antistatic high-hardness coating.

10. Use of the antistatic high-hardness coating according to any one of claims 1 to 8 in airplanes and high-speed railways.

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