Anti-static high-hardness coating and preparation process thereof

Abstract

The present application relates to the technical field of paint, and particularly relates to a kind of anti-static high-hardness paint and its preparation process.Concretely, it is composed of A component and B component, wherein A component includes by weight parts: water-based epoxy resin emulsion 80-100 parts, dispersing agent 1-2 parts, KH550 1-2 parts, cyclodextrin modified g-C3N4 / ATO composite nanomaterial 5-30 parts;B component includes by weight parts: water-based curing agent 20-50 parts, curing accelerator 1-3 parts.In the present application, cyclodextrin modified g-C3N4 has good chemical stability and adsorption, and after being combined with ATO nanoparticles, not only gives the paint anti-static property, but also can improve its hardness and adhesion.The preparation process is simple, the production efficiency is high, and large-scale production can be realized quickly.By adjusting the ratio of A component and B component, the performance of the paint can be flexibly controlled to meet the needs of different application scenarios.The paint in the present application has good anti-static property and can be used in the fields of aircraft, high-speed rail, etc.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of coatings, in particular to a kind of antistatic high hardness coating and preparation process thereof. BACKGROUND

[0002] As a functional material, the market demand of coatings is also growing. Conductive coatings are particularly concerned due to their special properties. It is widely used in electronics, construction, automotive, aerospace and other fields, such as electromagnetic shielding and heat dissipation coating in electronic devices, lightning protection and electromagnetic shielding in the construction field, vehicle body painting and interior anti-static in the automotive industry, and surface performance improvement 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 different conductive fillers, which are suitable for different application scenarios. In the future, conductive coatings will develop towards high performance, environmental protection and multifunctionalization to meet the growing market demand.

[0003] Antimony tin oxide (ATO) can be used as an antistatic additive. It is a conductive material with excellent performance, with good conductivity, transparency and chemical stability. In antistatic coatings, antimony tin oxide can effectively dissipate static charge and prevent static accumulation. In addition, it also has high transparency, with very weak absorption rate of visible light, which does not affect the transparency of the coating. Therefore, antimony tin oxide is widely used in coatings, plastics, textiles and other fields to improve the antistatic performance of materials.

[0004] In the prior art "A novel core-shell silica@graphene straticulate structured antistatic anticorrosion composite coating", ATO and reduced graphene oxide and functionalized silica are used together to improve the corrosion resistance and antistatic performance of the coating, but there is little research on improving the hardness and other properties of the coating. SUMMARY

[0005] To solve the problems in the prior art, the present application provides an antistatic high hardness coating and a preparation process thereof.

[0006] The present application is realized by the following technical solutions:

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

[0008] The B component comprises, by weight parts: 20~50 parts of water-based curing agent, 1~3 parts of curing accelerator.

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

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

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

[0012] Further, the curing accelerator is one of isophorone diamine and 2-ethyl-4-methyl imidazole.

[0013] Further, the curing accelerator is isophorone diamine.

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

[0015] The ATO nanoparticles and the cyclodextrin modified g-C3N4 nanocomposite are mixed at a mass ratio of 1:1, then immersed in 50 mL of ethanol and ultrasonically treated for 2 h; then the mixed solution is dried at 90 degrees Celsius for 24 h, and then heat treated at 150 degrees Celsius for 3 h, to obtain the cyclodextrin modified g-C3N4 / ATO composite nanomaterial after cooling.

[0016] Further, the preparation method of the ATO nanoparticles is as follows: 18.54 mmol of SnCl4, 2.5 mmol of SbCl3, 12 g of ammonium bicarbonate, and 4 g of acetic acid are added to 100 mL of anhydrous ethanol, the pH is adjusted to 7 using 25%wt% NH4OH, and stirring is performed for 4 h, then the precipitate is obtained by centrifugation, the precipitate is washed with deionized water for 3 times, and then the precipitate is heated in a muffle furnace at 550 degrees Celsius for 8 h, and after natural cooling, the ATO nanoparticles are obtained.

[0017] Further, the preparation method of the cyclodextrin modified g-C3N4 nanocomposite is as follows: 4 g of cyclodextrin is added to 50 mL of DMF, then 0.75 g of KH560 is added, and stirring is performed for 6 h; then 2 g of g-C3N4 is added and stirring is performed for 12 h, the precipitate is obtained by centrifugation, and the precipitate is washed with ethanol and deionized water respectively, and then dried at 80 degrees Celsius for 12 h, to obtain the cyclodextrin modified g-C3N4 nanocomposite.

[0018] The application further provides a preparation process of the anti-static high-hardness coating, which comprises the following steps: fully mixing the A component and the B component, stirring, and then ultrasonically dispersing, to obtain the anti-static high-hardness coating.

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

[0020] The g-C3N4 modified by the cyclodextrin in the present application has good chemical stability and adsorption, and after being combined with the ATO nanoparticles, not only the coating is endowed with antistatic property, but also its hardness and adhesion can be 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 A component and the B component, the performance of the coating can be flexibly controlled to meet the needs of different application scenarios. BRIEF DESCRIPTION OF DRAWINGS

[0021] The accompanying drawings, which are included to provide a further understanding of the embodiments of the application and are incorporated in and constitute a part of this application, illustrate embodiments of the application and together with the description serve to explain the principles of the application.

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

[0023] In order to make the objects, technical solutions and advantages of the present application clearer, further detailed description will be made to the present application in combination with embodiments and drawings, and the schematic embodiments of the present application and the description thereof are only used to explain the present application, and do not limit the present application.

[0024] Preparation method of the ATO nanoparticles in the present application:

[0025] Take 18.54 mmol SnCl4, 2.5 mmol SbCl3, 12 g ammonium bicarbonate and 4 g acetic acid into 100 mL anhydrous ethanol, adjust the pH to 7 using 25%wt% NH4OH, stir for 4 h, then centrifuge to obtain the precipitate, wash the precipitate with deionized water for 3 times, then heat the precipitate in a muffle furnace at 550 degrees Celsius for 8 h, and after natural cooling, the ATO nanoparticles are obtained.

[0026] Preparation method of the g-C3N4 in the present application:

[0027] Heat the melamine in a muffle furnace at 550 degrees Celsius for 3 h, after natural cooling, grind the obtained powder into fine powder, heat again at 550 degrees Celsius for 3 h, then wash the precipitate with 0.1M nitric acid and deionized water respectively, and then dry at 80°C for 6 h to obtain the g-C3N4.

[0028] Preparation of the g-C3N4 / ATO composite nanomaterial in the present application:

[0029] Mix ATO nanoparticles and g-C3N4 at a mass ratio of 1:1, then immerse in 50 mL of ethanol for 2 h of ultrasonic; then dry the mixed solution at 90 degrees Celsius for 24 h, then heat treat at 150°C for 3 h, and after cooling, obtain g-C3N4 / ATO composite nanomaterial.

[0030] Preparation of g-C3N4 nanocomposite modified by cyclodextrin in the application:

[0031] Take 4 g of cyclodextrin and add to 50 mL of DMF, then add 0.75 g of KH560 and stir for 6 h; then add 2 g of g-C3N4 and stir for 12 h, centrifuge to obtain a precipitate, wash the precipitate with ethanol and deionized water respectively, then dry at 80 degrees Celsius for 12 h, to obtain g-C3N4 nanocomposite modified by cyclodextrin.

[0032] Preparation of g-C3N4 / ATO composite nanomaterial modified by cyclodextrin in the application:

[0033] Mix ATO nanoparticles and g-C3N4 / ATO composite nanomaterial modified by cyclodextrin at a mass ratio of 1:1, then immerse in 50 mL of ethanol for 2 h of ultrasonic; then dry the mixed solution at 90 degrees Celsius for 24 h, then heat treat at 150°C for 3 h, and after cooling, obtain g-C3N4 / ATO composite nanomaterial modified by cyclodextrin, Figure 1 TEM image of g-C3N4 / ATO composite nanomaterial modified by cyclodextrin.

[0034] Example 1: Anti-static high-hardness coating

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

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

[0037] A method for preparing an anti-static high-hardness coating: add g-C3N4 / ATO composite nanomaterial modified by cyclodextrin to water-based epoxy resin emulsion, then stir for 5 min, then add KH550 and dispersant sodium dodecyl sulfonate, stir for 5 min, to obtain A component;

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

[0039] Mix A component and B component thoroughly, stir for 20 min, then ultrasonic dispersion for 10 min, to obtain an anti-static high-hardness coating.

[0040] Example 2

[0041] An antistatic high-hardness coating, A component: water-based epoxy resin emulsion 100 parts, dispersing agent sodium dodecyl sulfonate 1 part, KH550 2 parts, cyclodextrin modified g-C3N4 / ATO composite nanomaterial 10 parts;

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

[0043] A preparation method of an antistatic high-hardness coating: cyclodextrin modified g-C3N4 / ATO composite nanomaterial is added to water-based epoxy resin emulsion, then stirred for 5 min, then KH550 and dispersing agent sodium dodecyl sulfonate are added, and stirred for 5 min to obtain A component;

[0044] Water-based curing agent T31 and isophorone diamine are mixed and stirred for 5 min to obtain B component;

[0045] A component and B component are mixed thoroughly, stirred for 20 min, and then ultrasonically dispersed for 10 min to obtain the antistatic high-hardness coating.

[0046] Example 3

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

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

[0049] A preparation method of an antistatic high-hardness coating: cyclodextrin modified g-C3N4 / ATO composite nanomaterial is added to water-based epoxy resin emulsion, then stirred for 5 min, then KH550 and dispersing agent sodium dodecyl sulfonate are added, and stirred for 5 min to obtain A component;

[0050] Water-based curing agent T31 and isophorone diamine are mixed and stirred for 5 min to obtain B component;

[0051] A component and B component are mixed thoroughly, stirred for 20 min, and then ultrasonically dispersed for 10 min to obtain the antistatic high-hardness coating.

[0052] Example 4

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

[0054] Group B: water-based curing agent T3140 parts, isophorone diamine 1 part;

[0055] A kind of preparation method of antistatic high hardness coating: adding cyclodextrin modified g-C3N4 / ATO composite nanomaterial in water-based epoxy resin emulsion, then stirring 5min, then adding KH550 and dispersing agent sodium dodecyl sulfonate, stirring 5min, to obtain A component;

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

[0057] Mix A component and B component, after stirring 20min, ultrasonic dispersion 10min, to obtain antistatic high hardness coating.

[0058] Example 5

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

[0060] Group B: water-based curing agent T3140 parts, isophorone diamine 1 part;

[0061] A kind of preparation method of antistatic high hardness coating: adding cyclodextrin modified g-C3N4 / ATO composite nanomaterial in water-based epoxy resin emulsion, then stirring 5min, then adding KH550 and dispersing agent sodium dodecyl sulfonate, stirring 5min, to obtain A component;

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

[0063] Mix A component and B component, after stirring 20min, ultrasonic dispersion 10min, to obtain antistatic high hardness coating.

[0064] Example 6

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

[0066] Group B: water-based curing agent T3140 parts, isophorone diamine 1 part;

[0067] A preparation method of an anti-static high-hardness coating: adding g-C3N4 / ATO composite nanomaterials into water-based epoxy resin emulsion, then stirring for 5 min, then adding KH550 and dispersant sodium dodecyl sulfonate, stirring for 5 min, to obtain component A;

[0068] Mixing water-based curing agent T31 and isophorone diamine, stirring for 5 min, to obtain component B;

[0069] Mixing component A and component B thoroughly, stirring for 20 min, then ultrasonic dispersion for 10 min, to obtain the anti-static high-hardness coating.

[0070] Comparative example 1

[0071] An anti-static high-hardness coating, component A: water-based epoxy resin emulsion 100 parts, dispersant sodium dodecyl sulfonate 1 part, KH550 2 parts, ATO nanomaterial 20 parts;

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

[0073] A preparation method of an anti-static high-hardness coating: adding g-C3N4 / ATO composite nanomaterials into water-based epoxy resin emulsion, then stirring for 5 min, then adding KH550 and dispersant sodium dodecyl sulfonate, stirring for 5 min, to obtain component A;

[0074] Mixing water-based curing agent T31 and isophorone diamine, stirring for 5 min, to obtain component B;

[0075] Mixing component A and component B thoroughly, stirring for 20 min, then ultrasonic dispersion for 10 min, to obtain the anti-static high-hardness coating.

[0076] Comparative example 2

[0077] An anti-static high-hardness coating, component A: water-based epoxy resin emulsion 100 parts, dispersant sodium dodecyl sulfonate 1 part, KH550 2 parts, ATO nanomaterial 20 parts;

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

[0079] A preparation method of an anti-static high-hardness coating: adding g-C3N4 / ATO composite nanomaterials into water-based epoxy resin emulsion, then stirring for 5 min, then adding KH550 and dispersant sodium dodecyl sulfonate, stirring for 5 min, to obtain component A;

[0080] Mixing water-based curing agent T31 and isophorone diamine, stirring for 5 min, to obtain component B;

[0081] The A component and the B component are mixed well, stirred for 20 min, and ultrasonically dispersed for 10 min to obtain the antistatic high-hardness coating.

[0082] Test Example 1

[0083] The tinplate sheet is polished with 600-1000# sandpaper in sequence, and then ultrasonically cleaned with acetone and deionized water, respectively, and dried for standby use. The coating prepared in each example and the comparative example is uniformly coated on the treated tinplate sheet, and the coating thickness is about 100 μm. After coating, the test sheet is placed in an oven, dried at 40 degrees Celsius for 10 h, and prepared.

[0084] The hardness of the coating is tested according to the Shore hardness tester A. The adhesion of the coating is tested according to GB / T 1720 paint film adhesion. The surface resistance is tested by the surface resistance of the sample sheet of the heavy hammer type surface resistance tester.

[0085] Table 1 Performance test

[0086]

[0087] As can be seen from Table 1, the addition of cyclodextrin modified g-C3N4 / ATO composite nanomaterial in the coating has better hardness than g-C3N4 / ATO composite nanomaterial and ATO alone at the same content. The cyclodextrin modified g-C3N4 / ATO composite nanomaterial can better adsorb in the network structure formed by the epoxy resin, play a certain supporting role, and the cyclodextrin modified g-C3N4 / ATO composite nanomaterial itself is also easier to disperse uniformly in the coating, improving the hardness of the coating. ATO in the form of cyclodextrin modified g-C3N4 / ATO composite nanomaterial is better dispersed in the coating, improving the conductivity.

[0088] The above specific embodiments further illustrate the purpose, technical solutions and beneficial effects of the present application. It should be understood that the above description is only a specific embodiment of the present application and is not intended to limit the protection scope of the present application. Any modification, equivalent replacement, improvement, etc. within the spirit and principles of the present application shall be included in the protection scope of the present application.

Claims

1. An antistatic high-hardness coating, characterized in that, It consists of component A and component B, wherein component A includes, 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 nanomaterials; Component B comprises, by weight: 20-50 parts of water-based curing agent and 1-3 parts of curing accelerator; 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 at a mass ratio of 1:1 and then immersed in 50 mL of ethanol and sonicated for 2 h. The mixture was then dried at 90 °C for 24 h and then heat-treated at 150 °C for 3 h. After cooling, cyclodextrin-modified g-C3N4 / ATO composite nanomaterials were obtained.

2. The antistatic high-hardness coating according to claim 1, characterized in that, The dispersant in component A is selected from sodium dodecyl 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 component B is selected from phenolic modified fatty amine epoxy curing agents.

4. The antistatic high-hardness coating according to claim 3, characterized in that, The water-based curing agent in component B 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 1, characterized in that, The ATO nanoparticles were prepared as follows: 18.54 mmol SnCl4, 2.5 mmol SbCl3, 12 g ammonium bicarbonate and 4 g acetic acid were added to 100 mL anhydrous ethanol, the pH was adjusted to 7 with 25 wt% NH4OH, the mixture was stirred for 4 h, and then centrifuged to obtain a precipitate. The precipitate was washed three times with deionized water, and then heated in a muffle furnace at 550 degrees Celsius for 8 h. After natural cooling, ATO nanoparticles were obtained.

7. The antistatic high-hardness coating according to claim 6, characterized in that, The preparation method of the cyclodextrin-modified g-C3N4 nanocomposite is as follows: 4g of cyclodextrin is added to 50mL of DMF, then 0.75g of KH560 is added and stirred for 6h; then 2g of g-C3N4 is added and stirred for 12h, centrifuged to obtain a precipitate, the precipitate is washed with ethanol and deionized water respectively, and then dried at 80 degrees Celsius for 12h to obtain the cyclodextrin-modified g-C3N4 nanocomposite.

8. A preparation process for an antistatic high-hardness coating as described in any one of claims 1 to 7, characterized in that, Includes the following steps: Components A and B are thoroughly mixed, stirred, and then ultrasonically dispersed to obtain an antistatic, high-hardness coating.

Images