Modified graphene melamine antistatic coating solution

Abstract

This invention belongs to the field of functional coatings, specifically relating to a modified graphene melamine antistatic coating liquid and its preparation method. The modified graphene melamine antistatic coating liquid comprises the following raw materials in parts by weight: 20-40 parts polyurethane acrylate resin; 10-30 parts UV monomer diluent; 0.2-3 parts modified graphene melamine antistatic agent; 2-5 parts photoinitiator; 0.1-0.4 parts leveling agent; and the balance organic solvent. The modified graphene melamine antistatic coating liquid is obtained by high-speed dispersion and filtration. Through formulation design and the use of a self-made modified graphene melamine antistatic agent, the modified graphene melamine antistatic coating liquid of this invention can effectively improve the shortcomings of existing UV coating liquids, such as poor antistatic effect, easy migration and precipitation, and poor persistence, while also possessing properties such as low migration and high wear resistance.

Description

Technical Field

[0001] This invention belongs to the field of functional coatings, specifically relating to a modified graphene melamine antistatic coating liquid. Background Technology

[0002] Polymer materials are widely used in daily life due to their various excellent properties. However, because polymer materials have a relatively high volume resistivity, they are prone to generating static electricity during use. Since the surface conductivity of polymer materials is generally greater than their volume conductivity, surface conduction becomes the primary way for them to dissipate charge. Generally, we can prevent the accumulation of static electricity by increasing the surface conductivity or volume conductivity of the material to enable it to quickly dissipate the static charge generated during use. Commonly used antistatic methods for polymer materials include three types: adding antistatic agents, blending with other conductive molecules, and adding conductive fillers.

[0003] However, among the three methods mentioned above, adding antistatic agents can lead to migration, resulting in limited service life, poor heat resistance, or poor antistatic effect; blending with other conductive molecules can cause compatibility issues with the main resin, thus affecting various properties; and finally, adding conductive fillers generally requires a large amount, which directly affects the performance of the product. All of these methods have their shortcomings to varying degrees.

[0004] An antistatic coating refers to applying a layer of antistatic polymer coating to the surface of an object to eliminate static electricity. The main requirements for antistatic coatings include transparency or light color and a surface resistivity of less than 10 ohms. 10 With its high Ω / sq, stable surface resistivity, and absence of heavy metals, antistatic coatings have become the preferred solution in the antistatic field. However, even with antistatic liquid coatings, the migration and precipitation of antistatic additives in the components can still occur, resulting in poor longevity.

[0005] Furthermore, graphene has become a new choice for conductive fillers due to its high electrical conductivity, high specific surface area, and nanoscale flexible sheet structure. Melamine, however, possesses a triazine structure with a large number of lone pairs of electrons, preventing it from forming a conductive network and limiting its application in antistatic fields. Considering the application potential and performance advantages of graphene, and the structural characteristics of melamine, developing a modified graphene-melamine antistatic coating solution is a logical step. Summary of the Invention

[0006] The purpose of this invention is to address the shortcomings of existing UV coatings, such as poor antistatic effect, easy migration and precipitation, and poor persistence, by providing a modified graphene-melamine antistatic coating and its preparation method. Through formulation design and the use of a self-made modified graphene-melamine antistatic agent, these problems are solved while exhibiting properties such as low migration and high wear resistance.

[0007] To achieve the above objectives, the technical solution adopted by the present invention to solve its technical problem is as follows:

[0008] A modified graphene melamine antistatic coating liquid comprises the following raw materials in parts by weight:

[0009] 20-40 parts of polyurethane acrylate resin;

[0010] 10-30 parts of UV monomer diluent;

[0011] 0.2-3 parts of modified graphene melamine antistatic agent;

[0012] 2-5 parts of photoinitiator;

[0013] Leveling agent 0.1-0.4 parts;

[0014] Organic solvent balance.

[0015] Preferably, the UV monomer diluent is one or more of PETA, EO-TMPTA, PO-TMPTA, PDDA, NPGDA, DPGDA, HEA, and IBOMA.

[0016] Preferably, the modified graphene melamine antistatic agent is prepared by the following method:

[0017] (1) Take graphene oxide and N,N-dimethylformamide A and place them in a three-necked flask equipped with a stirrer. After sonicating for 2 hours at an ultrasonic power of 200W, place the three-necked flask in a water bath at 80℃, add IPDI, and react for 4 hours. Then, adjust the temperature to 60-80℃, add a reducing agent, and stir for 5-12 hours. After the reaction is completed, filter the product and wash it with dichloromethane. Dry the filter cake in a vacuum at 40℃ for 24 hours to obtain intermediate product I.

[0018] The ratio of graphene oxide, N,N-dimethylformamide A, IPDI, reducing agent, and dichloromethane is: 1g:200mL:1.5g:1-3g:600mL;

[0019] The hydroxyl content of the graphene oxide is 5 mmol / g;

[0020] (2) Intermediate product I and amino-dodecyl polyethylene glycol-carboxylic acid were placed in N,N-dimethylformamide B and stirred at room temperature for 2-4 hours. After the reaction was completed, the mixture was distilled under reduced pressure and dried under vacuum at 80°C for 4 hours to obtain intermediate product II.

[0021] The ratio of intermediate product I, amino-dodecyl polyethylene glycol-carboxylic acid, and N,N-dimethylformamide B is 2.2 g : 5-6 mmol : 500 mL;

[0022] (3) Dissolve a mixture of perfluorooctanoic acid, dicyclohexylcarbodiimide and 4-dimethylaminopyridine in N,N-dimethylformamide C and place it in a constant pressure dropping funnel. Slowly add the mixture to N,N-dimethylformamide D containing melamine. Stir magnetically at room temperature for 10-20 h, let stand, filter, distill under reduced pressure, and dry under vacuum at 80 °C for 4 h to obtain intermediate product III.

[0023] The ratio of perfluorooctanoic acid, dicyclohexylcarbodiimide, N,N-dimethylformamide C, melamine, and N,N-dimethylformamide D is 1.2 mmol: 1.2 mmol: 50 mL: 1 mmol: 40 mL;

[0024] The amount of 4-dimethylaminopyridine used is 1 wt% of the total mass of the reactants;

[0025] (4) Dissolve ethyl isocyanate of methacrylate and p-hydroxyanisole in N,N-dimethylformamide E and place them in a constant pressure dropping funnel. Slowly add the solution to N,N-dimethylformamide F containing intermediate product III. Stir magnetically for 1-2 hours at room temperature. After the reaction is complete, distill under reduced pressure and dry under vacuum at room temperature for 12 hours to obtain intermediate product IV.

[0026] The ratio of isocyanate methacrylate, N,N-dimethylformamide E, intermediate product III, and N,N-dimethylformamide F is 1.2 mmol: 30 mL: 1 mmol: 40 mL.

[0027] The amount of p-hydroxyanisole used is 1 wt% of the mass of isocyanate methacrylate;

[0028] (5) Dissolve intermediate product II, intermediate product IV, p-hydroxyanisole, dicyclohexylcarbodiimide, and 4-dimethylaminopyridine in N,N-dimethylformamide G, stir magnetically for 10-20 h at room temperature, let stand, filter, distill under reduced pressure, and dry under vacuum at 30°C for 12 h to obtain target product V.

[0029] The ratio of intermediate product II, intermediate product IV, dicyclohexylcarbodiimide, and N,N-dimethylformamide G is 5.2 g: 6 mmol: 6 mmol: 500 mL;

[0030] The amount of 4-dimethylaminopyridine used is 1 wt% of the total mass of the reactants;

[0031] The amount of p-hydroxyanisole used is 1 wt% of the mass of intermediate product IV.

[0032] Preferably, the reducing agent is phenylhydrazine or hydrazine hydrate.

[0033] Preferably, the photoinitiator is one or more of BP, 184, 1173 or TPO.

[0034] Preferably, the organic solvent is one or more of MIBK, EAc, BAc, PM, and PMA.

[0035] A method for preparing a modified graphene-melamine antistatic coating liquid includes the following steps:

[0036] Protect from light and keep the humidity ≤60%. After mixing the leveling agent and organic solvent evenly, add polyurethane acrylate resin, UV monomer diluent, and modified graphene melamine antistatic agent to the mixed solvent in sequence. After stirring evenly, add the photoinitiator and stir evenly. Filter with a filter cloth with a pore size of 1μm to obtain the modified graphene melamine antistatic coating liquid.

[0037] The modified graphene-melamine antistatic agent provided in this invention is prepared via the following process:

[0038]

[0039] The present invention has the following beneficial effects:

[0040] (1) The present invention provides a modified graphene melamine antistatic coating liquid, the main resin of which is polyurethane acrylate resin. On the one hand, polyurethane acrylate has excellent adhesion to commonly used PET, PC, PMMA and other substrates; on the other hand, the molecular design of polyurethane structure is strong and has excellent wear resistance.

[0041] (2) This invention provides a modified graphene melamine antistatic coating liquid, one of its components being a modified graphene melamine antistatic agent, whose molecular structure contains graphene, polyurethane, polyurea, ethoxy, melamine, acryloyloxy, and fluorine elements. First, graphene is a highly conductive nanoscale flexible sheet-like material that can form conductive networks in the matrix material, exhibiting excellent antistatic effects. Second, the ethoxy and melamine structures possess lone pairs of O and N electrons and have a certain degree of hygroscopicity, which can form conductive channels on the coating surface, thereby providing antistatic properties. Third, the presence of polyurethane and polyurea structures ensures excellent compatibility with the host resin, thereby improving optical performance. Fourth, the presence of a large amount of fluorine elements, due to the low surface tension of fluorine, allows the antistatic agent to accumulate on the surface, enhancing the antistatic effect. Fifth, the presence of acryloyloxy structures, in addition to having advantages in compatibility with the host resin, can also bond to the host resin during UV curing, exhibiting non-migration properties, causing no pollution to the production line, extending the service life of products, and ensuring high safety. Detailed implementation method:

[0042] The present invention will be described in detail below with reference to embodiments. However, it should be understood that the following embodiments are merely illustrative examples of implementation of the present invention and are not intended to limit the scope of the present invention.

[0043] The polyurethane acrylate resin used in the following embodiments of the present invention is CN965NS.

[0044] The leveling agent used in the following embodiments of the present invention is 401LS.

[0045] Example 1

[0046] A modified graphene melamine antistatic coating liquid comprises the following raw materials in parts by weight:

[0047] 30 parts of polyurethane acrylate resin;

[0048] PO-TMPTA 10 servings;

[0049] 5 copies of DPGDA;

[0050] 5 copies of IBOMA;

[0051] 1.5 parts of modified graphene melamine antistatic agent;

[0052] 1843 parts of photoinitiator;

[0053] 0.3 parts leveling agent;

[0054] EAc 25.2 copies;

[0055] 20 copies.

[0056] The above-mentioned modified graphene melamine antistatic agent is prepared by the following method:

[0057] (1) Graphene oxide and N,N-dimethylformamide A were placed in a three-necked flask equipped with a stirrer. After sonication at 200W for 2 hours, the three-necked flask was placed in a water bath at 80℃. IPDI was added and the reaction was carried out for 4 hours. Then, the temperature was adjusted to 60℃ and phenylhydrazine was added and stirred for 5 hours. After the reaction was completed, the product was filtered and washed with dichloromethane. The filter cake was dried under vacuum at 40℃ for 24 hours to obtain intermediate product I.

[0058] The ratio of graphene oxide, N,N-dimethylformamide A, IPDI, phenylhydrazine, and dichloromethane is 1g:200mL:1.5g:2g:600mL;

[0059] The hydroxyl content of the graphene oxide is 5 mmol / g;

[0060] Its infrared data is as follows: 3440cm -1-OH disappears; 2275cm -1 -NCO exists; 2953cm -1 -CH exists; 3350cm -1 1720cm -1 : Carbamate present; 3445cm -1 1730cm -1 Carboxyl groups are present; 1220cm -1 1105cm -1 The epoxy groups disappear.

[0061] (2) Intermediate product I and amino-dodecyl polyethylene glycol-carboxylic acid were placed in N,N-dimethylformamide B and stirred at room temperature for 3 hours. After the reaction was completed, the mixture was distilled under reduced pressure and dried under vacuum at 80°C for 4 hours to obtain intermediate product II.

[0062] The ratio of intermediate product I, amino-dodecyl polyethylene glycol-carboxylic acid, and N,N-dimethylformamide B is 2.2 g: 5.5 mmol: 500 mL.

[0063] Its infrared data is as follows: 2275cm -1 -NCO disappeared; 2953cm -1 -CH exists; 3350cm -1 1720cm -1 : Carbamate present; 3314cm -1 1677cm -1 : Amide bond present, 3445cm -1 1730cm -1 Carboxyl groups are present.

[0064] (3) Dissolve a mixture of perfluorooctanoic acid, dicyclohexylcarbodiimide and 4-dimethylaminopyridine in N,N-dimethylformamide C and place it in a constant pressure dropping funnel. Slowly add the mixture to N,N-dimethylformamide D containing melamine. Stir magnetically for 18 h at room temperature, let stand, filter, distill under reduced pressure, and dry under vacuum at 80 °C for 4 h to obtain intermediate product III.

[0065] The ratio of perfluorooctanoic acid, dicyclohexylcarbodiimide, N,N-dimethylformamide C, melamine, and N,N-dimethylformamide D is 1.2 mmol: 1.2 mmol: 50 mL: 1 mmol: 40 mL;

[0066] The amount of 4-dimethylaminopyridine used is 1 wt% of the total mass of the reactants;

[0067] Its infrared data is as follows: 1398cm -1 1462cm -11558cm -1 1593cm -1 Triazine ring present; 3321 cm -1 1675cm -1 Amide bonds are present; 3451 cm -1 -OH groups disappear; 3356cm -1 -NH2 is present; 1272 cm -1 :-CF exists.

[0068] (4) Dissolve ethyl isocyanate of methacrylate and p-hydroxyanisole in N,N-dimethylformamide E and place them in a constant pressure dropping funnel. Slowly add the solution to N,N-dimethylformamide F containing intermediate product III. Stir magnetically for 2 hours at room temperature. After the reaction is complete, distill under reduced pressure and dry under vacuum at room temperature for 12 hours to obtain intermediate product IV.

[0069] The ratio of isocyanate methacrylate, N,N-dimethylformamide E, intermediate product III, and N,N-dimethylformamide F is 1.2 mmol: 30 mL: 1 mmol: 40 mL.

[0070] The amount of p-hydroxyanisole used is 1 wt% of the mass of isocyanate methacrylate;

[0071] Its infrared data is as follows: 1398cm -1 1462cm -1 1558cm -1 1593cm -1 Triazine ring present; 3320 cm -1 1674cm -1 : Amide bonds are present and enhanced; 3356cm -1 -NH2 is present and its intensity decreases; 2275cm -1 :-NCO disappeared; 1609cm -1 810cm -1 -C = C- exists; 1272cm -1 :-CF exists.

[0072] (5) Intermediate product II, intermediate product IV, p-hydroxyanisole, dicyclohexylcarbodiimide, and 4-dimethylaminopyridine were dissolved in N,N-dimethylformamide G. The mixture was magnetically stirred at room temperature for 18 h, allowed to stand, filtered, and then vacuum distilled and dried at 30 °C for 12 h to obtain the target product V.

[0073] The ratio of intermediate product II, intermediate product IV, dicyclohexylcarbodiimide, and N,N-dimethylformamide G is 5.2 g: 6 mmol: 6 mmol: 500 mL;

[0074] The amount of 4-dimethylaminopyridine used is 1 wt% of the total mass of the reactants;

[0075] The amount of p-hydroxyanisole used is 1 wt% of the mass of intermediate product IV;

[0076] Its infrared data is as follows: 1398cm -1 1462cm -1 1558cm -1 1593cm -1 Triazine ring present; 2953 cm -1 -CH exists; 3315cm -1 1673cm -1 : Amide bonds are present and enhanced; 3356cm -1 -NH2 disappears; 3445cm -1 1730cm -1 The carboxyl group disappears; 3350cm -1 1720cm -1 : Carbamate present; 1609cm -1 810cm -1 -C = C- exists; 1272cm -1 :-CF exists.

[0077] Example 2

[0078] A modified graphene melamine antistatic coating liquid comprises the following raw materials in parts by weight:

[0079] 35 parts of polyurethane acrylate resin;

[0080] 8 copies of EO-TMPTA;

[0081] 10 copies of PDDA;

[0082] 7 copies of IBOMA;

[0083] Two parts of modified graphene melamine antistatic agent;

[0084] 11,734 parts of photoinitiator;

[0085] 0.4 parts leveling agent;

[0086] 12 servings of MIBK;

[0087] EAc 21.6 copies.

[0088] The above-mentioned modified graphene melamine antistatic agent is prepared by the following method:

[0089] (1) Graphene oxide and N,N-dimethylformamide A were placed in a three-necked flask equipped with a stirrer. After sonication at 200W for 2 hours, the three-necked flask was placed in a water bath at 80℃. IPDI was added and the reaction was carried out for 4 hours. Then, the temperature was adjusted to 80℃ and hydrazine hydrate was added and stirred for 12 hours. After the reaction was completed, the product was filtered and washed with dichloromethane. The filter cake was dried under vacuum at 40℃ for 24 hours to obtain intermediate product I.

[0090] The ratio of graphene oxide, N,N-dimethylformamide A, IPDI, hydrazine hydrate, and dichloromethane is 1g:200mL:1.5g:1g:600mL;

[0091] The hydroxyl content of the graphene oxide is 5 mmol / g;

[0092] Its infrared data is as follows: 3440cm -1 -OH disappears; 2275cm -1 -NCO exists; 2953cm -1 -CH exists; 3350cm -1 1720cm -1 : Carbamate present; 3445cm -1 1730cm -1 Carboxyl groups are present; 1220cm -1 1105cm -1 The epoxy groups disappear.

[0093] (2) Intermediate product I and amino-dodecyl polyethylene glycol-carboxylic acid were placed in N,N-dimethylformamide B and stirred at room temperature for 2 hours. After the reaction was completed, the mixture was distilled under reduced pressure and dried under vacuum at 80°C for 4 hours to obtain intermediate product II.

[0094] The ratio of intermediate product I, amino-dodecyl polyethylene glycol-carboxylic acid, and N,N-dimethylformamide B is 2.2 g: 6 mmol: 500 mL.

[0095] Its infrared data is as follows: 2275cm -1 -NCO disappeared; 2953cm -1 -CH exists; 3350cm -1 1720cm -1 : Carbamate present; 3314cm -1 1677cm -1 : Amide bond present, 3445cm -1 1730cm -1 Carboxyl groups are present.

[0096] (3) Dissolve a mixture of perfluorooctanoic acid, dicyclohexylcarbodiimide and 4-dimethylaminopyridine in N,N-dimethylformamide C and place it in a constant pressure dropping funnel. Slowly add the mixture to N,N-dimethylformamide D containing melamine. Stir magnetically for 20 h at room temperature, let stand, filter, distill under reduced pressure, and dry under vacuum at 80 °C for 4 h to obtain intermediate product III.

[0097] The ratio of perfluorooctanoic acid, dicyclohexylcarbodiimide, N,N-dimethylformamide C, melamine, and N,N-dimethylformamide D is 1.2 mmol: 1.2 mmol: 50 mL: 1 mmol: 40 mL;

[0098] The amount of 4-dimethylaminopyridine used is 1 wt% of the total mass of the reactants;

[0099] Its infrared data is as follows: 1398cm -1 1462cm -1 1558cm -1 1593cm -1 Triazine ring present; 3321 cm -1 1675cm -1 Amide bonds are present; 3451 cm -1 -OH groups disappear; 3356cm -1 -NH2 is present; 1272 cm -1 :-CF exists.

[0100] (4) Dissolve ethyl isocyanate of methacrylate and p-hydroxyanisole in N,N-dimethylformamide E and place them in a constant pressure dropping funnel. Slowly add the solution to N,N-dimethylformamide F containing intermediate product III. Stir magnetically for 2 hours at room temperature. After the reaction is complete, distill under reduced pressure and dry under vacuum at room temperature for 12 hours to obtain intermediate product IV.

[0101] The ratio of isocyanate methacrylate, N,N-dimethylformamide E, intermediate product III, and N,N-dimethylformamide F is 1.2 mmol: 30 mL: 1 mmol: 40 mL.

[0102] The amount of p-hydroxyanisole used is 1 wt% of the mass of isocyanate methacrylate;

[0103] Its infrared data is as follows: 1398cm -1 1462cm -1 1558cm -1 1593cm -1 Triazine ring present; 3320 cm -1 1674cm -1: Amide bonds are present and enhanced; 3356cm -1 -NH2 is present and its intensity decreases; 2275cm -1 :-NCO disappeared; 1609cm -1 810cm -1 -C = C- exists; 1272cm -1 :-CF exists.

[0104] (5) Intermediate product II, intermediate product IV, p-hydroxyanisole, dicyclohexylcarbodiimide, and 4-dimethylaminopyridine were dissolved in N,N-dimethylformamide G. The mixture was magnetically stirred at room temperature for 20 h, allowed to stand, filtered, and then vacuum distilled and dried at 30 °C for 12 h to obtain the target product V.

[0105] The ratio of intermediate product II, intermediate product IV, dicyclohexylcarbodiimide, and N,N-dimethylformamide G is 5.2 g: 6 mmol: 6 mmol: 500 mL;

[0106] The amount of 4-dimethylaminopyridine used is 1 wt% of the total mass of the reactants;

[0107] The amount of p-hydroxyanisole used is 1 wt% of the mass of intermediate product IV;

[0108] Its infrared data is as follows: 1398cm -1 1462cm -1 1558cm -1 1593cm -1 Triazine ring present; 2953 cm -1 -CH exists; 3315cm -1 1673cm -1 : Amide bonds are present and enhanced; 3356cm -1 -NH2 disappears; 3445cm -1 1730cm -1 The carboxyl group disappears; 3350cm -1 1720cm -1 : Carbamate present; 1609cm -1 810cm -1 -C = C- exists; 1272cm -1 :-CF exists.

[0109] Example 3

[0110] A modified graphene melamine antistatic coating liquid comprises the following raw materials in parts by weight:

[0111] 40 parts of polyurethane acrylate resin;

[0112] 5 portions of EO-TMPTA;

[0113] 15 NPGDA copies;

[0114] HEA 10 copies;

[0115] 3 parts of modified graphene melamine antistatic agent;

[0116] Photoinitiator BP 3 parts;

[0117] 1842 parts of photoinitiator;

[0118] 0.4 parts leveling agent;

[0119] 15 servings of MIBK;

[0120] EAc 6.6 copies.

[0121] The above-mentioned modified graphene melamine antistatic agent is prepared by the following method:

[0122] (1) Graphene oxide and N,N-dimethylformamide A were placed in a three-necked flask equipped with a stirrer. After sonication at 200W for 2 hours, the three-necked flask was placed in a water bath at 80℃. IPDI was added and the reaction was carried out for 4 hours. Then, the temperature was adjusted to 70℃ and phenylhydrazine was added and stirred for 5 hours. After the reaction was completed, the product was filtered and washed with dichloromethane. The filter cake was dried under vacuum at 40℃ for 24 hours to obtain intermediate product I.

[0123] The ratio of graphene oxide, N,N-dimethylformamide A, IPDI, phenylhydrazine, and dichloromethane is 1g:200mL:1.5g:3g:600mL;

[0124] The hydroxyl content of the graphene oxide is 5 mmol / g;

[0125] Its infrared data is as follows: 3440cm -1 -OH disappears; 2275cm -1 -NCO exists; 2953cm -1 -CH exists; 3350cm -1 1720cm -1 : Carbamate present; 3445cm -1 1730cm -1 Carboxyl groups are present; 1220cm -1 1105cm -1 The epoxy groups disappear.

[0126] (2) Intermediate product I and amino-dodecyl polyethylene glycol-carboxylic acid were placed in N,N-dimethylformamide B and stirred at room temperature for 4 hours. After the reaction was completed, the mixture was distilled under reduced pressure and dried under vacuum at 80°C for 4 hours to obtain intermediate product II.

[0127] The ratio of intermediate product I, amino-dodecyl polyethylene glycol-carboxylic acid, and N,N-dimethylformamide B is 2.2 g: 5 mmol: 500 mL.

[0128] Its infrared data is as follows: 2275cm -1 -NCO disappeared; 2953cm -1 -CH exists; 3350cm -1 1720cm -1 : Carbamate present; 3314cm -1 1677cm -1 : Amide bond present, 3445cm -1 1730cm -1 Carboxyl groups are present.

[0129] (3) Dissolve a mixture of perfluorooctanoic acid, dicyclohexylcarbodiimide and 4-dimethylaminopyridine in N,N-dimethylformamide C and place it in a constant pressure dropping funnel. Slowly add the mixture to N,N-dimethylformamide D containing melamine. Stir magnetically for 15 h at room temperature, let stand, filter, distill under reduced pressure, and dry under vacuum at 80 °C for 4 h to obtain intermediate product III.

[0130] The ratio of perfluorooctanoic acid, dicyclohexylcarbodiimide, N,N-dimethylformamide C, melamine, and N,N-dimethylformamide D is 1.2 mmol: 1.2 mmol: 50 mL: 1 mmol: 40 mL;

[0131] The amount of 4-dimethylaminopyridine used is 1 wt% of the total mass of the reactants;

[0132] Its infrared data is as follows: 1398cm -1 1462cm -1 1558cm -1 1593cm -1 Triazine ring present; 3321 cm -1 1675cm -1 Amide bonds are present; 3451 cm -1 -OH groups disappear; 3356cm -1 -NH2 is present; 1272 cm -1 :-CF exists.

[0133] (4) Dissolve ethyl isocyanate of methacrylate and p-hydroxyanisole in N,N-dimethylformamide E and place them in a constant pressure dropping funnel. Slowly add the solution to N,N-dimethylformamide F containing intermediate product III. Stir magnetically for 2 hours at room temperature. After the reaction is complete, distill under reduced pressure and dry under vacuum at room temperature for 12 hours to obtain intermediate product IV.

[0134] The ratio of isocyanate methacrylate, N,N-dimethylformamide E, intermediate product III, and N,N-dimethylformamide F is 1.2 mmol: 30 mL: 1 mmol: 40 mL.

[0135] The amount of p-hydroxyanisole used is 1 wt% of the mass of isocyanate methacrylate;

[0136] Its infrared data is as follows: 1398cm -1 1462cm -1 1558cm -1 1593cm -1 Triazine ring present; 3320 cm -1 1674cm -1 : Amide bonds are present and enhanced; 3356cm -1 -NH2 is present and its intensity decreases; 2275cm -1 :-NCO disappeared; 1609cm -1 810cm -1 -C = C- exists; 1272cm -1 :-CF exists.

[0137] (5) Intermediate product II, intermediate product IV, p-hydroxyanisole, dicyclohexylcarbodiimide, and 4-dimethylaminopyridine were dissolved in N,N-dimethylformamide G. The mixture was magnetically stirred at room temperature for 15 h, allowed to stand, filtered, and then vacuum distilled and dried at 30 °C for 12 h to obtain the target product V.

[0138] The ratio of intermediate product II, intermediate product IV, dicyclohexylcarbodiimide, and N,N-dimethylformamide G is 5.2 g: 6 mmol: 6 mmol: 500 mL;

[0139] The amount of 4-dimethylaminopyridine used is 1 wt% of the total mass of the reactants;

[0140] The amount of p-hydroxyanisole used is 1 wt% of the mass of intermediate product IV;

[0141] Its infrared data is as follows: 1398cm -1 1462cm -1 1558cm -1 1593cm-1 Triazine ring present; 2953 cm -1 -CH exists; 3315cm -1 1673cm -1 : Amide bonds are present and enhanced; 3356cm -1 -NH2 disappears; 3445cm -1 1730cm -1 The carboxyl group disappears; 3350cm -1 1720cm -1 : Carbamate present; 1609cm -1 810cm -1 -C = C- exists; 1272cm -1 :-CF exists.

[0142] Example 4

[0143] A modified graphene melamine antistatic coating liquid comprises the following raw materials in parts by weight:

[0144] 25 parts of polyurethane acrylate resin;

[0145] PO-TMPTA 8 parts;

[0146] 6 copies of PDDA;

[0147] Two IBOMA servings;

[0148] 0.5 parts of modified graphene melamine antistatic agent;

[0149] 1842 parts of photoinitiator;

[0150] 0.2 parts leveling agent;

[0151] 20 copies of BAc;

[0152] EAc 27.3 copies;

[0153] 10 copies of PMA.

[0154] The above-mentioned modified graphene melamine antistatic agent is prepared by the following method:

[0155] (1) Graphene oxide and N,N-dimethylformamide A were placed in a three-necked flask equipped with a stirrer. After sonication at 200W for 2 hours, the three-necked flask was placed in a water bath at 80℃. IPDI was added and the reaction was carried out for 4 hours. Then, the temperature was adjusted to 80℃ and hydrazine hydrate was added and stirred for 8 hours. After the reaction was completed, the product was filtered and washed with dichloromethane. The filter cake was dried under vacuum at 40℃ for 24 hours to obtain intermediate product I.

[0156] The ratio of graphene oxide, N,N-dimethylformamide A, IPDI, hydrazine hydrate, and dichloromethane is 1g:200mL:1.5g:2g:600mL;

[0157] The hydroxyl content of the graphene oxide is 5 mmol / g;

[0158] Its infrared data is as follows: 3440cm -1 -OH disappears; 2275cm -1 -NCO exists; 2953cm -1 -CH exists; 3350cm -1 1720cm -1 : Carbamate present; 3445cm -1 1730cm -1 Carboxyl groups are present; 1220cm -1 1105cm -1 The epoxy groups disappear.

[0159] (2) Intermediate product I and amino-dodecyl polyethylene glycol-carboxylic acid were placed in N,N-dimethylformamide B and stirred at room temperature for 3 hours. After the reaction was completed, the mixture was distilled under reduced pressure and dried under vacuum at 80°C for 4 hours to obtain intermediate product II.

[0160] The ratio of intermediate product I, amino-dodecyl polyethylene glycol-carboxylic acid, and N,N-dimethylformamide B is 2.2 g: 5 mmol: 500 mL.

[0161] Its infrared data is as follows: 2275cm -1 -NCO disappeared; 2953cm -1 -CH exists; 3350cm -1 1720cm -1 : Carbamate present; 3314cm -1 1677cm -1 : Amide bond present, 3445cm -1 1730cm -1 Carboxyl groups are present.

[0162] (3) Dissolve a mixture of perfluorooctanoic acid, dicyclohexylcarbodiimide and 4-dimethylaminopyridine in N,N-dimethylformamide C and place it in a constant pressure dropping funnel. Slowly add the mixture to N,N-dimethylformamide D containing melamine. Stir magnetically for 10 h at room temperature, let stand, filter, distill under reduced pressure, and dry under vacuum at 80 °C for 4 h to obtain intermediate product III.

[0163] The ratio of perfluorooctanoic acid, dicyclohexylcarbodiimide, N,N-dimethylformamide C, melamine, and N,N-dimethylformamide D is 1.2 mmol: 1.2 mmol: 50 mL: 1 mmol: 40 mL;

[0164] The amount of 4-dimethylaminopyridine used is 1 wt% of the total mass of the reactants;

[0165] Its infrared data is as follows: 1398cm -1 1462cm -1 1558cm -1 1593cm -1 Triazine ring present; 3321 cm -1 1675cm -1 Amide bonds are present; 3451 cm -1 -OH groups disappear; 3356cm -1 -NH2 is present; 1272 cm -1 :-CF exists.

[0166] (4) Dissolve ethyl isocyanate of methacrylate and p-hydroxyanisole in N,N-dimethylformamide E and place them in a constant pressure dropping funnel. Slowly add the solution to N,N-dimethylformamide F containing intermediate product III. Stir magnetically for 2 hours at room temperature. After the reaction is complete, distill under reduced pressure and dry under vacuum at room temperature for 12 hours to obtain intermediate product IV.

[0167] The ratio of isocyanate methacrylate, N,N-dimethylformamide E, intermediate product III, and N,N-dimethylformamide F is 1.2 mmol: 30 mL: 1 mmol: 40 mL.

[0168] The amount of p-hydroxyanisole used is 1 wt% of the mass of isocyanate methacrylate;

[0169] Its infrared data is as follows: 1398cm -1 1462cm -1 1558cm -1 1593cm -1 Triazine ring present; 3320 cm -1 1674cm -1 : Amide bonds are present and enhanced; 3356cm -1 -NH2 is present and its intensity decreases; 2275cm -1 :-NCO disappeared; 1609cm -1 810cm -1 -C = C- exists; 1272cm -1 :-CF exists.

[0170] (5) Intermediate product II, intermediate product IV, p-hydroxyanisole, dicyclohexylcarbodiimide, and 4-dimethylaminopyridine were dissolved in N,N-dimethylformamide G. The mixture was magnetically stirred at room temperature for 10 h, allowed to stand, filtered, and then vacuum distilled and dried at 30 °C for 12 h to obtain the target product V.

[0171] The ratio of intermediate product II, intermediate product IV, dicyclohexylcarbodiimide, and N,N-dimethylformamide G is 5.2 g: 6 mmol: 6 mmol: 500 mL;

[0172] The amount of 4-dimethylaminopyridine used is 1 wt% of the total mass of the reactants;

[0173] The amount of p-hydroxyanisole used is 1 wt% of the mass of intermediate product IV;

[0174] Its infrared data is as follows: 1398cm -1 1462cm -1 1558cm -1 1593cm -1 Triazine ring present; 2953 cm -1 -CH exists; 3315cm -1 1673cm -1 : Amide bonds are present and enhanced; 3356cm -1 -NH2 disappears; 3445cm -1 1730cm -1 The carboxyl group disappears; 3350cm -1 1720cm -1 : Carbamate present; 1609cm -1 810cm -1 -C = C- exists; 1272cm -1 :-CF exists.

[0175] Example 5

[0176] A modified graphene melamine antistatic coating liquid comprises the following raw materials in parts by weight:

[0177] 20 parts of polyurethane acrylate resin;

[0178] PETA 5 copies;

[0179] 20 copies of DPGDA;

[0180] Two IBOMA servings;

[0181] 0.2 parts of modified graphene melamine antistatic agent;

[0182] Photoinitiator TPO 2 parts;

[0183] 0.1 parts leveling agent;

[0184] 30 copies of BAc;

[0185] EAc 37.7 copies.

[0186] The above-mentioned modified graphene melamine antistatic agent is prepared by the following method:

[0187] (1) Graphene oxide and N,N-dimethylformamide A were placed in a three-necked flask equipped with a stirrer. After sonication at 200W for 2 hours, the three-necked flask was placed in a water bath at 80℃. IPDI was added and the reaction was carried out for 4 hours. Then, the temperature was adjusted to 60℃ and phenylhydrazine was added and stirred for 5 hours. After the reaction was completed, the product was filtered and washed with dichloromethane. The filter cake was dried under vacuum at 40℃ for 24 hours to obtain intermediate product I.

[0188] The ratio of graphene oxide, N,N-dimethylformamide A, IPDI, phenylhydrazine, and dichloromethane is 1g:200mL:1.5g:2g:600mL;

[0189] The hydroxyl content of the graphene oxide is 5 mmol / g;

[0190] Its infrared data is as follows: 3440cm -1 -OH disappears; 2275cm -1 -NCO exists; 2953cm -1 -CH exists; 3350cm -1 1720cm -1 : Carbamate present; 3445cm -1 1730cm -1 Carboxyl groups are present; 1220cm -1 1105cm -1 The epoxy groups disappear.

[0191] (2) Intermediate product I and amino-dodecyl polyethylene glycol-carboxylic acid were placed in N,N-dimethylformamide B and stirred at room temperature for 4 hours. After the reaction was completed, the mixture was distilled under reduced pressure and dried under vacuum at 80°C for 4 hours to obtain intermediate product II.

[0192] The ratio of intermediate product I, amino-dodecyl polyethylene glycol-carboxylic acid, and N,N-dimethylformamide B is 2.2 g: 5.5 mmol: 500 mL.

[0193] Its infrared data is as follows: 2275cm -1 -NCO disappeared; 2953cm -1 -CH exists; 3350cm-1 1720cm -1 : Carbamate present; 3314cm -1 1677cm -1 : Amide bond present, 3445cm -1 1730cm -1 Carboxyl groups are present.

[0194] (3) Dissolve a mixture of perfluorooctanoic acid, dicyclohexylcarbodiimide and 4-dimethylaminopyridine in N,N-dimethylformamide C and place it in a constant pressure dropping funnel. Slowly add the mixture to N,N-dimethylformamide D containing melamine. Stir magnetically for 18 h at room temperature, let stand, filter, distill under reduced pressure, and dry under vacuum at 80 °C for 4 h to obtain intermediate product III.

[0195] The ratio of perfluorooctanoic acid, dicyclohexylcarbodiimide, N,N-dimethylformamide C, melamine, and N,N-dimethylformamide D is 1.2 mmol: 1.2 mmol: 50 mL: 1 mmol: 40 mL;

[0196] The amount of 4-dimethylaminopyridine used is 1 wt% of the total mass of the reactants;

[0197] Its infrared data is as follows: 1398cm -1 1462cm -1 1558cm -1 1593cm -1 Triazine ring present; 3321 cm -1 1675cm -1 Amide bonds are present; 3451 cm -1 -OH groups disappear; 3356cm -1 -NH2 is present; 1272 cm -1 :-CF exists.

[0198] (4) Dissolve ethyl isocyanate of methacrylate and p-hydroxyanisole in N,N-dimethylformamide E and place them in a constant pressure dropping funnel. Slowly add the solution to N,N-dimethylformamide F containing intermediate product III. Stir magnetically for 2 hours at room temperature. After the reaction is complete, distill under reduced pressure and dry under vacuum at room temperature for 12 hours to obtain intermediate product IV.

[0199] The ratio of isocyanate methacrylate, N,N-dimethylformamide E, intermediate product III, and N,N-dimethylformamide F is 1.2 mmol: 30 mL: 1 mmol: 40 mL.

[0200] The amount of p-hydroxyanisole used is 1 wt% of the mass of isocyanate methacrylate;

[0201] Its infrared data is as follows: 1398cm -1 1462cm -1 1558cm -1 1593cm -1 Triazine ring present; 3320 cm -1 1674cm -1 : Amide bonds are present and enhanced; 3356cm -1 -NH2 is present and its intensity decreases; 2275cm -1 :-NCO disappeared; 1609cm -1 810cm -1 -C = C- exists; 1272cm -1 :-CF exists.

[0202] (5) Intermediate product II, intermediate product IV, p-hydroxyanisole, dicyclohexylcarbodiimide, and 4-dimethylaminopyridine were dissolved in N,N-dimethylformamide G. The mixture was magnetically stirred at room temperature for 18 h, allowed to stand, filtered, and then vacuum distilled and dried at 30 °C for 12 h to obtain the target product V.

[0203] The ratio of intermediate product II, intermediate product IV, dicyclohexylcarbodiimide, and N,N-dimethylformamide G is 5.2 g: 6 mmol: 6 mmol: 500 mL;

[0204] The amount of 4-dimethylaminopyridine used is 1 wt% of the total mass of the reactants;

[0205] The amount of p-hydroxyanisole used is 1 wt% of the mass of intermediate product IV;

[0206] Its infrared data is as follows: 1398cm -1 1462cm -1 1558cm -1 1593cm -1 Triazine ring present; 2953 cm -1 -CH exists; 3315cm -1 1673cm -1 : Amide bonds are present and enhanced; 3356cm -1 -NH2 disappears; 3445cm -1 1730cm -1 The carboxyl group disappears; 3350cm -1 1720cm -1 : Carbamate present; 1609cm -1 810cm -1 -C = C- exists; 1272cm -1 :-CF exists.

[0207] Example 6

[0208] A modified graphene melamine antistatic coating liquid comprises the following raw materials in parts by weight:

[0209] 30 parts of polyurethane acrylate resin;

[0210] PO-TMPTA 10 servings;

[0211] 5 NPGDA copies;

[0212] 5 IBOMA;

[0213] 1 part of modified graphene melamine antistatic agent;

[0214] 11,734 parts of photoinitiator;

[0215] 0.3 parts leveling agent;

[0216] 10 servings of MIBK;

[0217] EAc 24.7 copies;

[0218] 10 PM.

[0219] The above-mentioned modified graphene melamine antistatic agent is prepared by the following method:

[0220] (1) Graphene oxide and N,N-dimethylformamide A were placed in a three-necked flask equipped with a stirrer. After sonication at 200W for 2 hours, the three-necked flask was placed in a water bath at 80℃. IPDI was added and the reaction was carried out for 4 hours. Then, the temperature was adjusted to 80℃ and hydrazine hydrate was added and stirred for 12 hours. After the reaction was completed, the product was filtered and washed with dichloromethane. The filter cake was dried under vacuum at 40℃ for 24 hours to obtain intermediate product I.

[0221] The ratio of graphene oxide, N,N-dimethylformamide A, IPDI, hydrazine hydrate, and dichloromethane is 1g:200mL:1.5g:1g:600mL;

[0222] The hydroxyl content of the graphene oxide is 5 mmol / g;

[0223] Its infrared data is as follows: 3440cm -1 -OH disappears; 2275cm -1 -NCO exists; 2953cm -1 -CH exists; 3350cm -1 1720cm -1 : Carbamate present; 3445cm -1 1730cm-1 Carboxyl groups are present; 1220cm -1 1105cm -1 The epoxy groups disappear.

[0224] (2) Intermediate product I and amino-dodecyl polyethylene glycol-carboxylic acid were placed in N,N-dimethylformamide B and stirred at room temperature for 3 hours. After the reaction was completed, the mixture was distilled under reduced pressure and dried under vacuum at 80°C for 4 hours to obtain intermediate product II.

[0225] The ratio of intermediate product I, amino-dodecyl polyethylene glycol-carboxylic acid, and N,N-dimethylformamide B is 2.2 g: 6 mmol: 500 mL.

[0226] Its infrared data is as follows: 2275cm -1 -NCO disappeared; 2953cm -1 -CH exists; 3350cm -1 1720cm -1 : Carbamate present; 3314cm -1 1677cm -1 : Amide bond present, 3445cm -1 1730cm -1 Carboxyl groups are present.

[0227] (3) Dissolve a mixture of perfluorooctanoic acid, dicyclohexylcarbodiimide and 4-dimethylaminopyridine in N,N-dimethylformamide C and place it in a constant pressure dropping funnel. Slowly add the mixture to N,N-dimethylformamide D containing melamine. Stir magnetically for 20 h at room temperature, let stand, filter, distill under reduced pressure, and dry under vacuum at 80 °C for 4 h to obtain intermediate product III.

[0228] The ratio of perfluorooctanoic acid, dicyclohexylcarbodiimide, N,N-dimethylformamide C, melamine, and N,N-dimethylformamide D is 1.2 mmol: 1.2 mmol: 50 mL: 1 mmol: 40 mL;

[0229] The amount of 4-dimethylaminopyridine used is 1 wt% of the total mass of the reactants;

[0230] Its infrared data is as follows: 1398cm -1 1462cm -1 1558cm -1 1593cm -1 Triazine ring present; 3321 cm -1 1675cm -1 Amide bonds are present; 3451 cm -1 -OH groups disappear; 3356cm -1-NH2 is present; 1272 cm -1 :-CF exists.

[0231] (4) Dissolve ethyl isocyanate of methacrylate and p-hydroxyanisole in N,N-dimethylformamide E and place them in a constant pressure dropping funnel. Slowly add the solution to N,N-dimethylformamide F containing intermediate product III. Stir magnetically for 1 h at room temperature. After the reaction is complete, distill under reduced pressure and dry under vacuum at room temperature for 12 h to obtain intermediate product IV.

[0232] The ratio of isocyanate methacrylate, N,N-dimethylformamide E, intermediate product III, and N,N-dimethylformamide F is 1.2 mmol: 30 mL: 1 mmol: 40 mL.

[0233] The amount of p-hydroxyanisole used is 1 wt% of the mass of isocyanate methacrylate;

[0234] Its infrared data is as follows: 1398cm -1 1462cm -1 1558cm -1 1593cm -1 Triazine ring present; 3320 cm -1 1674cm -1 : Amide bonds are present and enhanced; 3356cm -1 -NH2 is present and its intensity decreases; 2275cm -1 :-NCO disappeared; 1609cm -1 810cm -1 -C = C- exists; 1272cm -1 :-CF exists.

[0235] (5) Intermediate product II, intermediate product IV, p-hydroxyanisole, dicyclohexylcarbodiimide, and 4-dimethylaminopyridine were dissolved in N,N-dimethylformamide G. The mixture was magnetically stirred at room temperature for 20 h, allowed to stand, filtered, and then vacuum distilled and dried at 30 °C for 12 h to obtain the target product V.

[0236] The ratio of intermediate product II, intermediate product IV, dicyclohexylcarbodiimide, and N,N-dimethylformamide G is 5.2 g: 6 mmol: 6 mmol: 500 mL;

[0237] The amount of 4-dimethylaminopyridine used is 1 wt% of the total mass of the reactants;

[0238] The amount of p-hydroxyanisole used is 1 wt% of the mass of intermediate product IV;

[0239] Its infrared data is as follows: 1398cm-1 1462cm -1 1558cm -1 1593cm -1 Triazine ring present; 2953 cm -1 -CH exists; 3315cm -1 1673cm -1 : Amide bonds are present and enhanced; 3356cm -1 -NH2 disappears; 3445cm -1 1730cm -1 The carboxyl group disappears; 3350cm -1 1720cm -1 : Carbamate present; 1609cm -1 810cm -1 -C = C- exists; 1272cm -1 :-CF exists.

[0240] The preparation method of the modified graphene melamine antistatic coating liquid described in Examples 1-6 above includes the following steps:

[0241] Protect from light and keep the humidity ≤60%. After mixing the leveling agent and organic solvent evenly, add polyurethane acrylate resin, UV monomer diluent, and modified graphene melamine antistatic agent to the mixed solvent in sequence. After stirring evenly, add the photoinitiator and stir evenly. Filter with a filter cloth with a pore size of 1μm to obtain the modified graphene melamine antistatic coating liquid.

[0242] Using the modified graphene melamine antistatic coating obtained in Specific Example 1 as the base material for the application example, it was made into a PET optical film hardening coating.

[0243] Application Example 1

[0244] A method for preparing a modified graphene-melamine antistatic coating, comprising the following steps:

[0245] The modified graphene-melamine antistatic coating was uniformly coated onto a PET film (50 μm thick), heated at 80°C for 120 s, and then subjected to UV irradiation with an energy of 400 mJ / cm². 2 An irradiation time of 30 seconds yielded a modified graphene-melamine antistatic coating with a dry film thickness of 1 μm.

[0246] The preparation methods of the modified graphene melamine antistatic coatings in Application Examples 2-6 are the same as those in Application Example 1, except that they are prepared using the modified graphene melamine antistatic coating liquids from their respective examples.

[0247] Application implementation comparison examples 1-5 are all compared with application example 1:

[0248] Application Implementation Comparison Example 1

[0249] A modified graphene melamine antistatic coating liquid comprises the following raw materials in parts by weight:

[0250] 30 parts of polyester acrylate resin CN2254NS;

[0251] PO-TMPTA 10 servings;

[0252] 5 copies of DPGDA;

[0253] 5 IBOMA;

[0254] 1.5 parts of modified graphene melamine antistatic agent;

[0255] 1843 parts of photoinitiator;

[0256] 0.3 parts leveling agent;

[0257] EAc 25.2 copies;

[0258] 20 copies.

[0259] The preparation method of the modified graphene melamine antistatic agent is the same as in Specific Example 1.

[0260] Application Implementation Comparison Example 2

[0261] A UV coating liquid comprises the following raw materials in parts by weight:

[0262] 30 parts of polyurethane acrylate resin;

[0263] PO-TMPTA 10 servings;

[0264] 5 copies of DPGDA;

[0265] 5 IBOMA;

[0266] 1843 parts of photoinitiator;

[0267] 0.3 parts leveling agent;

[0268] EAc 26.7 copies;

[0269] 20 copies.

[0270] Application Implementation Comparison Example 3

[0271] A modified melamine antistatic coating liquid comprises the following raw materials in parts by weight:

[0272] 30 parts of polyurethane acrylate resin;

[0273] PO-TMPTA 10 servings;

[0274] 5 copies of DPGDA;

[0275] 5 IBOMA;

[0276] 1.5 parts of modified melamine antistatic agent;

[0277] 1843 parts of photoinitiator;

[0278] 0.3 parts leveling agent;

[0279] EAc 25.2 copies;

[0280] 20 copies.

[0281] The preparation method of the modified melamine antistatic agent is the same as that of intermediate product IV in the specific examples.

[0282] Application Implementation Comparison Example 4

[0283] A graphene-modified melamine antistatic coating liquid comprises the following raw materials in parts by weight:

[0284] 30 parts of polyurethane acrylate resin;

[0285] PO-TMPTA 10 servings;

[0286] 5 copies of DPGDA;

[0287] 5 IBOMA;

[0288] 0.15 parts of graphene;

[0289] 1.35 parts of modified melamine antistatic agent;

[0290] 1843 parts of photoinitiator;

[0291] 0.3 parts leveling agent;

[0292] EAc 25.2 copies;

[0293] 20 copies.

[0294] The preparation method of the modified melamine antistatic agent is the same as that of intermediate product IV in the specific examples.

[0295] Application Implementation Comparison Example 5

[0296] A graphene antistatic coating liquid comprises the following raw materials in parts by weight:

[0297] 30 parts of polyurethane acrylate resin;

[0298] PO-TMPTA 10 servings;

[0299] 5 copies of DPGDA;

[0300] 5 IBOMA;

[0301] 1.5 parts graphene;

[0302] 1843 parts of photoinitiator;

[0303] 0.3 parts leveling agent;

[0304] EAc 25.2 copies;

[0305] 20 copies.

[0306] Application Implementation Comparison Example 6

[0307] A modified graphene antistatic coating liquid comprises the following raw materials in parts by weight:

[0308] 30 parts of polyurethane acrylate resin;

[0309] PO-TMPTA 10 servings;

[0310] 5 copies of DPGDA;

[0311] 5 copies of IBOMA;

[0312] 1.5 parts of modified graphene antistatic agent;

[0313] 1843 parts of photoinitiator;

[0314] 0.3 parts leveling agent;

[0315] EAc 25.2 copies;

[0316] 20 copies.

[0317] The preparation method of the modified graphene antistatic agent is the same as that of intermediate product II in specific example 1.

[0318] Application Implementation Comparison Example 7

[0319] A modified graphene melamine antistatic coating liquid comprises the following raw materials in parts by weight:

[0320] 30 parts of polyurethane acrylate resin;

[0321] PO-TMPTA 10 servings;

[0322] 5 copies of DPGDA;

[0323] 5 copies of IBOMA;

[0324] 1.5 parts of modified graphene melamine antistatic agent;

[0325] 1843 parts of photoinitiator;

[0326] 0.3 parts leveling agent;

[0327] EAc 25.2 copies;

[0328] 20 copies.

[0329] The above-mentioned modified graphene melamine antistatic agent is prepared by the following method:

[0330] (1) Graphene oxide and N,N-dimethylformamide A were placed in a three-necked flask equipped with a stirrer. After sonication at 200W for 2 hours, the three-necked flask was placed in a water bath at 80℃. IPDI was added and the reaction was carried out for 4 hours. Then, the temperature was adjusted to 60℃ and phenylhydrazine was added and stirred for 5 hours. After the reaction was completed, the product was filtered and washed with dichloromethane. The filter cake was dried under vacuum at 40℃ for 24 hours to obtain intermediate product I.

[0331] The ratio of graphene oxide, N,N-dimethylformamide A, IPDI, phenylhydrazine, and dichloromethane is 1g:200mL:1.5g:2g:600mL;

[0332] The hydroxyl content of the graphene oxide is 5 mmol / g;

[0333] Its infrared data is as follows: 3440cm -1 -OH disappears; 2275cm -1 -NCO exists; 2953cm -1 -CH exists; 3350cm -1 1720cm -1 : Carbamate present; 3445cm -1 1730cm -1 Carboxyl groups are present; 1220cm -1 1105cm -1 The epoxy groups disappear.

[0334] (2) Intermediate product I and amino-dodecyl polyethylene glycol-carboxylic acid were placed in N,N-dimethylformamide B and stirred at room temperature for 3 hours. After the reaction was completed, the mixture was distilled under reduced pressure and dried under vacuum at 80°C for 4 hours to obtain intermediate product II.

[0335] The ratio of intermediate product I, amino-dodecyl polyethylene glycol-carboxylic acid, and N,N-dimethylformamide B is 2.2 g: 5.5 mmol: 500 mL.

[0336] Its infrared data is as follows: 2275cm -1-NCO disappeared; 2953cm -1 -CH exists; 3350cm -1 1720cm -1 : Carbamate present; 3314cm -1 1677cm -1 : Amide bond present, 3445cm -1 1730cm -1 Carboxyl groups are present.

[0337] (3) Dissolve ethyl isocyanate of methacrylate and p-hydroxyanisole in N,N-dimethylformamide C and place them in a constant pressure dropping funnel. Slowly add the solution to N,N-dimethylformamide D containing melamine. Stir magnetically for 2 hours at room temperature. After the reaction is complete, distill under reduced pressure and dry under vacuum at room temperature for 12 hours to obtain intermediate product III.

[0338] The ratio of isocyanate methacrylate, N,N-dimethylformamide C, melamine, and N,N-dimethylformamide D is 1.2 mmol: 30 mL: 1 mmol: 40 mL.

[0339] The amount of p-hydroxyanisole used is 1 wt% of the mass of isocyanate methacrylate;

[0340] Its infrared data is as follows: 1398cm -1 1462cm -1 1558cm -1 1593cm -1 Triazine ring present; 3320 cm -1 1674cm -1 Amide bonds are present; 3356 cm⁻¹ -1 -NH2 is present and its intensity decreases; 2275cm -1 :-NCO disappeared; 1609cm -1 810cm -1 -C = C - exists.

[0341] (4) Intermediate product II, intermediate product III, p-hydroxyanisole, dicyclohexylcarbodiimide, and 4-dimethylaminopyridine were dissolved in N,N-dimethylformamide E. The mixture was magnetically stirred at room temperature for 18 hours, allowed to stand, filtered, and then vacuum distilled and dried at 30°C for 12 hours to obtain target product IV.

[0342] The ratio of intermediate product II, intermediate product III, dicyclohexylcarbodiimide, and N,N-dimethylformamide E is 10.4 g: 6 mmol: 6 mmol: 500 mL.

[0343] The amount of 4-dimethylaminopyridine used is 1 wt% of the total mass of the reactants;

[0344] The amount of p-hydroxyanisole used is 1 wt% of the mass of intermediate product III;

[0345] Its infrared data is as follows: 1398cm -1 1462cm -1 1558cm -1 1593cm -1 Triazine ring present; 2953 cm -1 -CH exists; 3315cm -1 1673cm -1 : Amide bonds are present and enhanced; 3356cm -1 -NH2 disappears; 3445cm -1 1730cm -1 The carboxyl group disappears; 3350cm -1 1720cm -1 : Carbamate present; 1609cm -1 810cm -1 -C = C - exists.

[0346] Application Implementation Comparison Example 8

[0347] A modified graphene melamine antistatic coating liquid comprises the following raw materials in parts by weight:

[0348] 30 parts of polyurethane acrylate resin;

[0349] PO-TMPTA 10 servings;

[0350] 5 copies of DPGDA;

[0351] 5 copies of IBOMA;

[0352] 1.5 parts of modified graphene melamine antistatic agent;

[0353] 1843 parts of photoinitiator;

[0354] 0.3 parts leveling agent;

[0355] EAc 25.2 copies;

[0356] 20 copies.

[0357] The above-mentioned modified graphene melamine antistatic agent is prepared by the following method:

[0358] (1) Graphene oxide and N,N-dimethylformamide A were placed in a three-necked flask equipped with a stirrer. After sonication at 200W for 2 hours, the three-necked flask was placed in a water bath at 80℃. IPDI was added and the reaction was carried out for 4 hours. Then, the temperature was adjusted to 60℃ and phenylhydrazine was added and stirred for 5 hours. After the reaction was completed, the product was filtered and washed with dichloromethane. The filter cake was dried under vacuum at 40℃ for 24 hours to obtain intermediate product I.

[0359] The ratio of graphene oxide, N,N-dimethylformamide A, IPDI, phenylhydrazine, and dichloromethane is 1g:200mL:1.5g:2g:600mL;

[0360] The hydroxyl content of the graphene oxide is 5 mmol / g;

[0361] Its infrared data is as follows: 3440cm -1 -OH disappears; 2275cm -1 -NCO exists; 2953cm -1 -CH exists; 3350cm -1 1720cm -1 : Carbamate present; 3445cm -1 1730cm -1 Carboxyl groups are present; 1220cm -1 1105cm -1 The epoxy groups disappear.

[0362] (2) Dissolve a mixture of perfluorooctanoic acid, dicyclohexylcarbodiimide and 4-dimethylaminopyridine in N,N-dimethylformamide B and place it in a constant pressure dropping funnel. Slowly add the mixture to N,N-dimethylformamide C containing melamine. Stir magnetically for 18 h at room temperature, let stand, filter, distill under reduced pressure, and dry under vacuum at 80 °C for 4 h to obtain intermediate product II.

[0363] The ratio of perfluorooctanoic acid, dicyclohexylcarbodiimide, N,N-dimethylformamide B, melamine, and N,N-dimethylformamide C is 1.2 mmol: 1.2 mmol: 50 mL: 1 mmol: 40 mL;

[0364] The amount of 4-dimethylaminopyridine used is 1 wt% of the total mass of the reactants;

[0365] Its infrared data is as follows: 1398cm -1 1462cm -1 1558cm -1 1593cm -1 Triazine ring present; 3321 cm -1 1675cm -1Amide bonds are present; 3451 cm -1 -OH groups disappear; 3356cm -1 -NH2 is present; 1272 cm -1 :-CF exists.

[0366] (3) Dissolve ethyl isocyanate of methacrylate and p-hydroxyanisole in N,N-dimethylformamide D and place them in a constant pressure dropping funnel. Slowly add the solution to N,N-dimethylformamide E containing intermediate product II. Stir magnetically for 2 hours at room temperature. After the reaction is completed, distill under reduced pressure and dry under vacuum at room temperature for 12 hours to obtain intermediate product III.

[0367] The ratio of isocyanate methacrylate, N,N-dimethylformamide D, intermediate product II, and N,N-dimethylformamide E is 1.2 mmol: 30 mL: 1 mmol: 40 mL.

[0368] The amount of p-hydroxyanisole used is 1 wt% of the mass of isocyanate methacrylate;

[0369] Its infrared data is as follows: 1398cm -1 1462cm -1 1558cm -1 1593cm -1 Triazine ring present; 3320 cm -1 1674cm -1 : Amide bonds are present and enhanced; 3356cm -1 -NH2 is present and its intensity decreases; 2275cm -1 :-NCO disappeared; 1609cm -1 810cm -1 -C = C- exists; 1272cm -1 :-CF exists.

[0370] (4) Intermediate product I and intermediate product III were placed in N,N-dimethylformamide F and stirred at room temperature for 3 hours. After the reaction was completed, the mixture was distilled under reduced pressure and dried under vacuum at 80°C for 4 hours to obtain target product IV.

[0371] The ratio of intermediate product I, intermediate product III, and N,N-dimethylformamide F is 4.4 g: 5.5 mmol: 500 mL;

[0372] Its infrared data is as follows: 1398cm -1 1462cm -1 1558cm -1 1593cm -1 Triazine ring present; 2953 cm -1-CH exists; 3315cm -1 1673cm -1 : Amide bonds are present and enhanced; 3356cm -1 -NH2 disappears; 2275cm -1 :-NCO disappeared; 3445cm -1 1730cm -1 Carboxyl groups are present; 3350cm -1 1720cm -1 : Carbamate present; 1609cm -1 810cm -1 -C = C- exists; 1272cm -1 :-CF exists.

[0373] Application Implementation Comparison Example 9

[0374] A modified graphene melamine antistatic coating liquid comprises the following raw materials in parts by weight:

[0375] 30 parts of polyurethane acrylate resin;

[0376] PO-TMPTA 10 servings;

[0377] 5 copies of DPGDA;

[0378] 5 copies of IBOMA;

[0379] 1.5 parts of modified graphene melamine antistatic agent;

[0380] 1843 parts of photoinitiator;

[0381] 0.3 parts leveling agent;

[0382] EAc 25.2 copies;

[0383] 20 copies.

[0384] The above-mentioned modified graphene melamine antistatic agent is prepared by the following method:

[0385] (1) Graphene oxide and N,N-dimethylformamide A were placed in a three-necked flask equipped with a stirrer. After sonication at 200W for 2 hours, the three-necked flask was placed in a water bath at 80℃. IPDI was added and the reaction was carried out for 4 hours. Then, the temperature was adjusted to 60℃ and phenylhydrazine was added and stirred for 5 hours. After the reaction was completed, the product was filtered and washed with dichloromethane. The filter cake was dried under vacuum at 40℃ for 24 hours to obtain intermediate product I.

[0386] The ratio of graphene oxide, N,N-dimethylformamide A, IPDI, phenylhydrazine, and dichloromethane is 1g:200mL:1.5g:2g:600mL;

[0387] The hydroxyl content of the graphene oxide is 5 mmol / g;

[0388] Its infrared data is as follows: 3440cm -1 -OH disappears; 2275cm -1 -NCO exists; 2953cm -1 -CH exists; 3350cm -1 1720cm -1 : Carbamate present; 3445cm -1 1730cm -1 Carboxyl groups are present; 1220cm -1 1105cm -1 The epoxy groups disappear.

[0389] (2) Intermediate product I and amino-dodecyl polyethylene glycol-carboxylic acid were placed in N,N-dimethylformamide B and stirred at room temperature for 3 hours. After the reaction was completed, the mixture was distilled under reduced pressure and dried under vacuum at 80°C for 4 hours to obtain intermediate product II.

[0390] The ratio of intermediate product I, amino-dodecyl polyethylene glycol-carboxylic acid, and N,N-dimethylformamide B is 2.2 g: 5.5 mmol: 500 mL.

[0391] Its infrared data is as follows: 2275cm -1 -NCO disappeared; 2953cm -1 -CH exists; 3350cm -1 1720cm -1 : Carbamate present; 3314cm -1 1677cm -1 : Amide bond present, 3445cm -1 1730cm -1 Carboxyl groups are present.

[0392] (3) Dissolve a mixture of perfluorooctanoic acid, dicyclohexylcarbodiimide and 4-dimethylaminopyridine in N,N-dimethylformamide C and place it in a constant pressure dropping funnel. Slowly add the mixture to N,N-dimethylformamide D containing melamine. Stir magnetically for 18 h at room temperature, let stand, filter, distill under reduced pressure, and dry under vacuum at 80 °C for 4 h to obtain intermediate product III.

[0393] The ratio of perfluorooctanoic acid, dicyclohexylcarbodiimide, N,N-dimethylformamide C, melamine, and N,N-dimethylformamide D is 1.2 mmol: 1.2 mmol: 50 mL: 1 mmol: 40 mL;

[0394] The amount of 4-dimethylaminopyridine used is 1 wt% of the total mass of the reactants;

[0395] Its infrared data is as follows: 1398cm -1 1462cm -1 1558cm -1 1593cm -1 Triazine ring present; 3321 cm -1 1675cm -1 Amide bonds are present; 3451 cm -1 -OH groups disappear; 3356cm -1 -NH2 is present; 1272 cm -1 :-CF exists.

[0396] (4) Intermediate product II, intermediate product III, p-hydroxyanisole, dicyclohexylcarbodiimide, and 4-dimethylaminopyridine were dissolved in N,N-dimethylformamide E. The mixture was magnetically stirred at room temperature for 18 hours, allowed to stand, filtered, and then vacuum distilled and dried at 30°C for 12 hours to obtain target product IV.

[0397] The ratio of intermediate product II, intermediate product III, dicyclohexylcarbodiimide, and N,N-dimethylformamide E is 10.4 g: 6 mmol: 6 mmol: 500 mL.

[0398] The amount of 4-dimethylaminopyridine used is 1 wt% of the total mass of the reactants;

[0399] The amount of p-hydroxyanisole used is 1 wt% of the mass of intermediate product III;

[0400] Its infrared data is as follows: 1398cm -1 1462cm -1 1558cm -1 1593cm -1 Triazine ring present; 2953 cm -1 -CH exists; 3315cm -1 1673cm -1 : Amide bonds are present and enhanced; 3356cm -1 -NH2 disappears; 3445cm -1 1730cm -1 The carboxyl group disappears; 3350cm -1 1720cm-1 : Carbamate present; 1272cm -1 :-CF exists.

[0401] The method for preparing an antistatic (UV) coating liquid as described in Comparative Examples 1-9 above includes the following steps:

[0402] Protect from light and keep the humidity ≤60%. After mixing the leveling agent and organic solvent evenly, add polyurethane acrylate resin, UV monomer diluent, and modified graphene melamine antistatic agent to the mixed solvent in sequence. After stirring evenly, add the photoinitiator and stir evenly. Filter with a filter cloth with a pore size of 1μm to obtain the corresponding antistatic (UV) coating liquid.

[0403] The antistatic (UV) coating solution described in Comparative Examples 1-9 above was applied to an optical film to prepare an antistatic (UV) coating. The preparation method includes the following specific steps:

[0404] The antistatic / UV coating solution was uniformly coated onto a PET film (50 μm thick), heated at 80°C for 120 s, and then subjected to UV irradiation with an energy of 400 mJ / cm². 2 An antistatic (UV) coating with a dry film thickness of 1 μm is obtained by irradiation time of 30 s.

[0405] The physical properties of the antistatic coatings prepared in Application Examples 1-6 and Comparative Examples 1-9 of this invention were measured respectively, and the results are shown in Table 1.

[0406] Table 1 Physical test performance of each application example

[0407]

[0408] First, compared with application examples 1-6 and application examples 1-9, the antistatic coating of the present invention has excellent antistatic properties and antistatic durability; and the optimal amount of the antistatic agent of the present invention is 1.5 parts.

[0409] Secondly, the modified graphene melamine antistatic coating of the present invention has good wear resistance; in addition, it also has the advantage of non-migration.

[0410] The testing method is as follows:

[0411] (1) Transmittance and haze: Tested according to the method described in JIS K7105-1981.

[0412] (2) Adhesion: Adhesion was tested according to the method described in ASTM D3359-17.

[0413] (3) Surface resistivity: Surface resistivity shall be tested in accordance with the method described in GB / T 1410-2006.

[0414] (4) Surface resistivity retest (antistatic durability): After testing according to GB / T 1410-2006 standard, the test sample is placed in a constant temperature and humidity chamber at 60±2℃ and 95±2% for 96h, and the resistivity data is tested again.

[0415] (5) Migration: The PET hardened film was soaked in acetonitrile for 24 hours. The soaking solution was taken and the ultraviolet-visible spectrum was measured. The wavelength range was set to 200-500 nm. The migration is expressed as follows: 5 is the lowest molar absorption coefficient, that is, the best migration; 1 is the highest molar absorption coefficient, that is, the worst migration.

[0416] (6) Abrasion resistance: Tested according to the method described in HG / T 4303-2012. Test conditions: 750g weight, 0000# steel wool.

[0417] Based on the above-described preferred embodiments of the present invention, and through the foregoing description, those skilled in the art can make various changes and modifications without departing from the inventive concept. The technical scope of this invention is not limited to the contents of the specification, but must be determined according to the scope of the claims.

Claims

1. A modified graphene-melamine antistatic coating liquid, characterized in that: It consists of the following parts by weight of raw materials: 20-40 parts of polyurethane acrylate resin; 10-30 parts UV monomer diluent; 0.2-3 parts of modified graphene melamine antistatic agent; Photoinitiator 2-5 parts; Leveling agent 0.1-0.4 parts; Organic solvent balance; The modified graphene melamine antistatic agent is prepared by the following method: (1) Take graphene oxide and N,N-dimethylformamide A and place them in a three-necked flask equipped with a stirrer. After sonicating for 2 hours at an ultrasonic power of 200W, place the three-necked flask in a water bath at 80℃, add IPDI, and react for 4 hours. Then, adjust the temperature to 60-80℃, add a reducing agent, and stir for 5-12 hours. After the reaction is completed, filter the product and wash it with dichloromethane. Dry the filter cake in a vacuum at 40℃ for 24 hours to obtain intermediate product I. The ratio of graphene oxide, N,N-dimethylformamide A, IPDI, reducing agent, and dichloromethane is: 1g:200mL:1.5g:1-3g:600mL; The hydroxyl content of the graphene oxide is 5 mmol / g; (2) Intermediate product I and amino-dodecyl polyethylene glycol-carboxylic acid were placed in N,N-dimethylformamide B and stirred at room temperature for 2-4 hours. After the reaction was completed, the mixture was distilled under reduced pressure and dried under vacuum at 80°C for 4 hours to obtain intermediate product II. The ratio of intermediate product I, amino-dodecyl polyethylene glycol-carboxylic acid, and N,N-dimethylformamide B is 2.2 g: 5-6 mmol: 500 mL; (3) Dissolve a mixture of perfluorooctanoic acid, dicyclohexylcarbodiimide and 4-dimethylaminopyridine in N,N-dimethylformamide C and place it in a constant pressure dropping funnel. Slowly add it dropwise to N,N-dimethylformamide D containing melamine. Stir magnetically at room temperature for 10-20 h, let stand, filter, distill under reduced pressure, and dry under vacuum at 80°C for 4 h to obtain intermediate product III; The ratio of perfluorooctanoic acid, dicyclohexylcarbodiimide, N,N-dimethylformamide C, melamine, and N,N-dimethylformamide D is 1.2 mmol: 1.2 mmol: 50 mL: 1 mmol: 40 mL; The amount of 4-dimethylaminopyridine used is 1 wt% of the total mass of the reactants; (4) Dissolve ethyl isocyanate of methacrylate and p-hydroxyanisole in N,N-dimethylformamide E and place them in a constant pressure dropping funnel. Slowly add the solution to N,N-dimethylformamide F containing intermediate product III. Stir magnetically for 1-2 hours at room temperature. After the reaction is complete, distill under reduced pressure and dry under vacuum at room temperature for 12 hours to obtain intermediate product IV. The ratio of isocyanate methacrylate, N,N-dimethylformamide E, intermediate product III, and N,N-dimethylformamide F is 1.2 mmol: 30 mL: 1 mmol: 40 mL. The amount of p-hydroxyanisole used is 1 wt% of the mass of isocyanate methacrylate; (5) Dissolve intermediate product II, intermediate product IV, p-hydroxyanisole, dicyclohexylcarbodiimide, and 4-dimethylaminopyridine in N,N-dimethylformamide G, stir magnetically for 10-20 h at room temperature, let stand, filter, distill under reduced pressure, and dry under vacuum at 30°C for 12 h to obtain target product V; The ratio of intermediate product II, intermediate product IV, dicyclohexylcarbodiimide, and N,N-dimethylformamide G is 5.2 g: 6 mmol: 6 mmol: 500 mL; The amount of 4-dimethylaminopyridine used is 1 wt% of the total mass of the reactants; The amount of p-hydroxyanisole used is 1 wt% of the mass of intermediate product IV.

2. The modified graphene melamine antistatic coating liquid according to claim 1, characterized in that: The UV monomer diluent is one or more of PETA, EO-TMPTA, PO-TMPTA, PDDA, NPGDA, DPGDA, HEA, and IBOMA.

3. The modified graphene melamine antistatic coating liquid according to claim 1, characterized in that: The reducing agent is phenylhydrazine or hydrazine hydrate.

4. The modified graphene melamine antistatic coating liquid according to claim 1, characterized in that: The photoinitiator is one or more of BP, 184, 1173 or TPO.

5. The modified graphene melamine antistatic coating liquid according to claim 1, characterized in that: The organic solvent is one or more of MIBK, EAc, BAc, PM, and PMA.

6. A method for preparing a modified graphene melamine antistatic coating liquid according to any one of claims 1-5, characterized in that: The steps include the following: Protect from light and keep the humidity ≤60%. After mixing the leveling agent and organic solvent evenly, add polyurethane acrylate resin, UV monomer diluent, and modified graphene melamine antistatic agent to the mixed solvent in sequence. After stirring evenly, add the photoinitiator and stir evenly. Filter with a filter cloth with a pore size of 1μm to obtain the modified graphene melamine antistatic coating liquid.

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