Ionomer coating for eliminating surface charges, preparation method thereof and corresponding coating

Abstract

The invention relates to an ionomer coating for eliminating surface charges. The ionomer coating comprises the following components: matrix resin; an acidic ionomer; the main cross-linking agent has a hydrogen bond group and a base group, the functionality of the base group is 1, the functionality of the hydrogen bond group is greater than or equal to 1, epoxy resin can be added as an auxiliary cross-linking agent, and the functionality of the epoxy resin is greater than or equal to 2; and a polar solvent. The invention also provides a preparation method of the corresponding ionomer coating and a coating. The ionomer coating for eliminating the surface charges, the preparation method of the ionomer coating and the corresponding coating have the beneficial effects that the service life can be greatly prolonged on the premise of not influencing the storage life and the coating performance of the acidic ionomer coating; the coating can be cured at low temperature to form a film and is suitable for a heat-labile plastic substrate; the paint can be prepared into water-based paint to reduce pollution; the method is low in raw material cost, convenient to implement and suitable for large-scale industrial application.

Description

[0001] This application is a divisional application of Chinese invention patent application No. CN202011578812.6, filed on December 28, 2020, entitled "Ionomer Coating for Eliminating Surface Charge, Preparation Method Thereof and Corresponding Coating". Technical Field

[0002] This invention relates to the field of polymer materials technology, and in particular to an ionomer coating for eliminating surface charge, its preparation method, and the corresponding coating. Background Technology

[0003] Ionic polymers are polymers of monomers with ionic bonds, mainly including polymers containing carboxyl groups or sulfonic acid groups. They possess a certain charge-transfer capability and can be blended into insulating polymer coatings to impart charge conductivity and eliminate the charge accumulated on the coating surface due to friction, such as... Figure 1 As shown.

[0004] Acidic ionomers are soluble in water or alcohol and can be blended with water-soluble or alcohol-soluble coatings to form coatings with good dispersibility and high transparency. Ionomers have better solubility and dispersion stability than graphite or metal powders, and the coatings are colorless and transparent, making them suitable for large-scale industrial applications. The properties of acidic ionomers can be adjusted by adding a small amount of basic compounds for partial neutralization. These basic compounds include: alkali metals, amino groups, quaternary ammonium bases, pyridine, pyridine derivatives, triazine, 2,4,6-triphenyl-1,3,5-triazine, imidazole, benzimidazole, benzotriazole, oxazole, and polymers with positively charged repeating units of the following formula (Ⅰ).

[0005] The basic compound can be used alone or in combination. The molar number of basic groups is less than the molar number of acidic groups on the ionomer.

[0006] Organic amines and basic aromatic heterocycles can increase the solubility of acidic ionomers in alcohol solvents and their compatibility with coatings. Besides small molecules, basic compounds can also be positively charged conjugated polymers, such as the polymer in formula (Ⅰ) above, which has a positive charge dispersed across multiple conjugated units. The 4-vinylbenzenesulfonic acid homopolymer partially neutralized with this polymer exhibits significantly improved charge conductivity, as shown in formula (Ⅱ) below.

[0007] These polymers can be incorporated into coatings in smaller quantities (less than 10%) to achieve the effect of eliminating surface charge.

[0008] However, acidic ionomers have inherent defects. Their ionic groups dissociate upon absorbing moisture. Due to the repulsion of like charges, the acidic ionomers separate through molecular chain peristalsis, creating microcracks within the coating film. This causes the film to change from transparent to whitish. These microcracks block charge transfer channels, rapidly diminishing the coating's ability to dissipate charge and significantly reducing its lifespan compared to normal paints. The lower the acidic ionomer content in the coating, the faster the charge conductivity decays, typically resulting in a lifespan of less than one year, failing to meet industrial performance requirements. Extending the lifespan of acidic ionomers requires overcoming the problem of internal cracking in the coating.

[0009] To mitigate the cracking tendency of acidic ionomer coatings, crosslinking agents are typically added, such as epoxy resins, isocyanates, melamine-formaldehyde resins, and multifunctional bases. However, highly reactive crosslinking agents that react at room temperature (such as isocyanates or multifunctional bases) can cause gelation in the coating, resulting in a short shelf life and unsuitability for use. Furthermore, most crosslinking agents (such as latent isocyanates, melamine-formaldehyde resins, and epoxy resins) require a reaction with acidic groups of 130°C–150°C, exceeding the glass transition temperature of commonly used plastic substrates, making them unusable on plastic substrates. Some patents (CN103348520A) address this by increasing the molecular weight of the ionomer to enhance entanglement. However, excessively high molecular weight polymers have excessive viscosity, reduced solubility, and difficulty in uniform coating. Coatings require polymers with a wide molecular weight distribution; low molecular weight polymers are necessary, so this method has limited effectiveness in improving microcracks in the coating.

[0010] Therefore, to date, there is no ideal solution that can simultaneously eliminate microcracks in the coating, extend its service life, and allow for low-temperature curing, making it suitable for coatings on plastic substrates. Summary of the Invention

[0011] This invention addresses the technical problems of acidic ionomer coatings being prone to microcracks and having a short service life by providing an ionomer coating for eliminating surface charge that effectively extends service life and can be cured at low temperatures on a plastic substrate, along with its preparation method and the corresponding coating.

[0012] To achieve the above objectives, the present invention provides the following technical solution for ionomer coatings used to eliminate surface charge: Includes the following components: Main resin; Acidic ionomers; The main crosslinking agent has both hydrogen bond groups and base groups, the functionality of its base groups is 1, the functionality of its hydrogen bond groups is ≥1, and epoxy resin can be added as an auxiliary crosslinking agent, the functionality of the epoxy resin is ≥2. Polar solvents.

[0013] Preferably, the base resin can be a common insulating coating, such as waterborne polyacrylate or waterborne polyurethane. The acidic ionomer is compatible with many water-soluble or alcohol-soluble resins, such as polyacrylate, polyurethane, cellulose, and polyvinyl acetal. Partially carboxyl-containing polyacrylates, partially carboxyl-containing polyurethanes, polyvinyl butyral, and cellulose are preferred.

[0014] Preferably, the acidic ionomer is a pure acidic ionomer or an acidic ionomer partially neutralized by a basic group.

[0015] Preferably, the acidic ionomer is selected from one or more homopolymers or copolymers formed from the following monomers: Acrylic acid, maleic acid, 4-vinylbenzenesulfonic acid, vinylsulfonic acid, That is, it can be: acrylic acid homopolymer, acrylic acid copolymer with other monomers, maleic acid copolymer with other monomers, 4-vinylbenzenesulfonic acid homopolymer, 4-vinylbenzenesulfonic acid copolymer with other monomers, vinyl sulfonic acid homopolymer, vinyl sulfonic acid copolymer with other monomers.

[0016] Preferably, the basic group is provided by one or more of the following basic compounds: Alkali metals, amino groups, quaternary ammonium bases, pyridine, pyridine derivatives, triazine, 2,4,6-triphenyl-1,3,5-triazine, imidazole, benzimidazole, benzotriazole, oxazole, and polymers with positively charged repeating units of the following formula (I). The number of moles of the basic groups is less than the number of moles of the acidic groups in the acidic ionomer.

[0017] Preferably, the acidic ionomer is poly4-vinylbenzenesulfonic acid, and the basic group is provided by a polymer with positively charged repeating units of the following formula (I). The number of moles of positively charged groups in the polymer of formula (Ⅰ) is less than the number of moles of acidic groups in the acidic ionomer.

[0018] Preferably, the crosslinking agent having both hydrogen-bonding groups and base groups is selected from one or more of the following compounds: Amines containing carbon hydroxyl groups, pyridines containing carbon hydroxyl groups, imidazoles containing carbon hydroxyl groups, benzimidazoles containing carbon hydroxyl groups, benzotriazoles containing carbon hydroxyl groups, melamines containing carbon hydroxyl groups, and 2,4,6-triphenyl-1,3-5-triazines containing carbon hydroxyl groups. Preferably, the crosslinking agent having both hydrogen-bonding groups and base groups is selected from one or more of the following compounds: Derivatives of 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, phenolic hydroxylated 2,4,6-triphenyl-1,3-5-triazine derivatives, diethanolamine, triethanolamine, tris(hydroxymethyl)aminomethane, bis(2-hydroxymethyl)amino-tris(hydroxymethyl)methane, N,N-dihydroxyethyldodecylamine, N,N-dihydroxyethyloctadecylamine, 2-hydroxymethylpyridine, 2-hydroxyethylpyridine, 2-pyridinepropanol, 2-pyridinebutanol, 3-hydroxypyridine, 3-hydroxymethylpyridine, 2-(3-pyridyl)ethanol, 1-(3-pyridyl)ethanol, 3-pyridinepropanol, 3-pyridinebutanol, 4- Hydroxypyridine, 4-hydroxymethylpyridine, 4-hydroxyethylpyridine, 4-pyridinepropanol, 4-pyridinebutanol, 1-(2-hydroxyethyl)imidazole, 1-hydroxymethylbenzimidazole, 4-hydroxybenzimidazole, 2-methyl-5-hydroxybenzimidazole, melamine, benzomelamine, 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-benzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-benzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-benzotriazole, 2-(2'-hydroxy-3',5'-dipentylphenyl) 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-bis(α,α-dimethylbenzyl)phenyl)benzotriazole, 2-(2H-benzotriazole-2-yl)-6-(dodecyl)-4-methylphenol, 2,4,6-tris(2,4-dihydroxyphenyl)-1,3,5-triazine, 2-(2,4-dihydroxyphenyl)-4,6-diphenyl-1,3,5-triazine, 2-(2,4-dihydroxyphenyl)-4,6-di(2,4-dimethylphenyl)-1,3,5-triazine, 2-[2,4-bis(2- ... Mixtures of 2-[4-dimethylphenyl)-2-(1,3,5-triazinyl)]5-octoxyphenol, octyltriazinone, 2-(4,6-diphenyl-1,3,5-triazin-2)-5-n-hexanoxyphenol, bis-ethylethoxyphenol methoxyphenyltriazine, 2-[4-[2-hydroxy-3-tetaneoxypropyl]oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2-[4-[2-hydroxy-3-dodecyloxypropyl]oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine; More preferably, the crosslinking agent having both hydrogen-bonding groups and base groups is selected from one or more of the following compounds: Diethanolamine, triethanolamine, tris(hydroxymethyl)aminomethane, bis(2-hydroxymethyl)amino-tris(hydroxymethyl)methane, N,N-dihydroxyethyldodecylamine, N,N-dihydroxyethyloctadecylamine, 2-hydroxymethylpyridine, 2-hydroxyethylpyridine, 2-pyridinepropanol, 2-pyridinebutanol, 3-hydroxypyridine, 3-hydroxymethylpyridine, 2-(3-pyridyl)ethanol, 1-(3-pyridyl)ethanol, 3-pyridinepropanol, 3-pyridinebutanol, 4-hydroxypyridine, 4-hydroxymethylpyridine, 4-hydroxyethylpyridine, 4-pyridinepropanol, 4-pyridinebutanol, 1- Hydroxymethylbenzimidazole, 4-hydroxybenzimidazole, 2-methyl-5-hydroxybenzimidazole, melamine, benzomelamine, 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-benzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)benzotriazole, 2- (2'-hydroxy-3',5'-bis(α,α-dimethylbenzyl)phenyl)benzotriazole, 2-(2H-benzotriazole-2-yl)-6-(dodecyl)-4-methylphenol, 2,4,6-tris(2,4-dihydroxyphenyl)-1,3,5-triazine, 2-(2,4-dihydroxyphenyl)-4,6-diphenyl-1,3,5-triazine, 2-(2,4-dihydroxyphenyl)-4,6-di(2,4-dimethylphenyl)-1,3,5-triazine, 2-[2,4-bis(2,4-dimethylphenyl)-2-(1,3, Mixtures of 5-triazinyl]5-octyloxyphenol, octyltriazinone, 2-(4,6-diphenyl-1,3,5-triazin-2)-5-n-hexaneoxyphenol, bis-ethylethoxyphenol methoxyphenyltriazine, 2-[4-[2-hydroxy-3-tetaneoxypropyl]oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2-[4-[2-hydroxy-3-dodecyloxypropyl]oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine.

[0019] The molar ratio of the monofunctional base group in the crosslinking agent containing both hydrogen-bonding and base groups to the acidic group in the acidic ionomer is 0.05 to 1.

[0020] Preferably, the ionomer coating for eliminating surface charge may also contain epoxy resin as an auxiliary crosslinking agent, with the epoxy group having a functionality ≥2. Preferably, the epoxy resin is selected from one or more of the following compounds: Bisphenol A type epoxy resin, bisphenol F type epoxy resin, polyphenol type glycidyl ether epoxy resin, aliphatic glycidyl ether epoxy resin, alicyclic epoxy resin, diglycidyl phthalate, hexahydrophthalic acid diglycidyl ether, epoxidized soybean oil, dimer acid diglycidyl ether, trimethylolpropane triglycidyl ether, glycerol triglycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, 4,5-epoxycyclohexane-1,2-dicarboxylic acid diglycidyl ether, 3,3'-(oxydimethylene)bis(3-ethyl)oxetane, 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexyl carboxylate, bis((3,4-epoxycyclohexyl)methyl)adipate, 1,4-cyclohexanediethanol (3,4-epoxycyclohexane carboxylate); Preferably, the molar ratio between the epoxy groups in the epoxy resin and the acidic groups in the acidic ionomer is 0 to 0.1.

[0021] In the ionomer coating for eliminating surface charge of the present invention, a main crosslinking agent with both hydrogen-bonding groups and monofunctional bases is used to stabilize acidic groups, and the attraction of ionic bonds and hydrogen bonds counteracts the repulsive forces between anions on the ionomer. Specifically, firstly, basic groups and hydrogen-bonding groups can stabilize the acidic groups on the ionomer. Acidic groups (such as sulfonic acid) themselves have certain oxidizing properties and are unstable, easily causing the film to yellow and discolor after film formation, resulting in decreased performance. After neutralization with basic groups to form salts, their stability is greatly improved. Hydrogen-bonding groups (such as hydroxyl groups) also have a stabilizing effect on acidic groups, which can effectively extend the service life of the ionomer. Secondly, bases and acidic groups can be directly bonded by ionic bonds, while hydrogen-bonding groups (such as hydroxyl, phenolic, and nitrogen-hydrogen groups) can be bonded to acidic groups through hydrogen bonds. The attraction of ionic bonds and hydrogen bonds counteracts the repulsive forces between anions on the ionomer, which can overcome the tendency for microcracks to form inside the coating film. Ionic bonds are strong binding forces; if the functionality exceeds 1, gelation will occur. Hydrogen bonds, on the other hand, are weaker, and increasing the functionality will not cause gelation. Both types of crosslinking can be achieved at room temperature without causing gelation. The crosslinking agent and the acidic ionomer can be co-soluble in the solvent, maintaining fluidity and good coating performance. After coating, low-temperature drying forms a crosslinked coating. The drying temperature is between room temperature and 85°C, which extends the service life while meeting the requirements for low-temperature curing, making it suitable for coating plastic substrates.

[0022] In addition to a main crosslinking agent containing both hydrogen-bonding groups and monofunctional bases, a small amount of epoxy resin can be added to assist crosslinking and eliminate microcracks generated inside the film. Typically, tertiary amines, imidazoles, benzimidazoles, pyridine bases, and their quaternary ammonium salts catalyze the ring-opening crosslinking reaction between epoxy resin and carboxyl groups. Without a catalyst, the reaction temperature between epoxy resin and the carboxyl groups on the acidic ionomer is above 120°C; with a catalyst, it can proceed at a lower temperature. Crosslinking agents containing both hydrogen-bonding groups and monofunctional bases themselves include structures such as tertiary amines, imidazoles, benzimidazoles, and pyridines. Furthermore, our experiments have shown that benzotriazole, melamine, and 2,4,6-triphenyl-1,3-5-triazine structures contained in crosslinking agents containing both hydrogen-bonding groups and base groups can also catalyze the ring-opening reaction between epoxy resin and carboxyl groups. Therefore, when a primary crosslinking agent containing both hydrogen-bonding groups and monofunctional bases is present, epoxy resin can participate in the reaction as an auxiliary crosslinking agent, curing into a film at low temperature. This is suitable for coating on plastic substrates and can be selectively added as needed.

[0023] In the ionomer coating for eliminating surface charge of the present invention, thickeners, antioxidants, anti-scratch agents and other additives may be added if necessary.

[0024] The present invention also provides a method for preparing the ionomer coating for eliminating surface charge as described in the claims, the preparation method comprising: The main resin and acidic ionomer are mixed evenly, and then a main crosslinking agent with both hydrogen bonding groups and base groups is added and dissolved in a polar solvent to obtain the ionomer coating for eliminating surface charge. Preferably, the preparation method includes adding epoxy resin and dissolving it in a polar solvent.

[0025] The polar solvent can be water, alcohols, N,N-dimethylformamide, or dimethyl sulfoxide, etc.

[0026] The present invention also provides a coating for eliminating surface charge, wherein the ionomer coating for eliminating surface charge is applied to a substrate, including a plastic substrate, by means of scraping, spraying, gravure printing or screen printing, and the solvent is dried to form the coating for eliminating surface charge.

[0027] The curing temperature of the coating is room temperature to 85°C, for example, 20°C to 85°C, which is suitable for coating flexible plastic substrates that are not resistant to high temperatures.

[0028] The volume resistivity or surface resistivity of the coating is in the range of 10. 6 Ohm ~ 10 9Between ohms. For coatings with waterborne polyacrylate or waterborne polyurethane as the main resin, the surface charge elimination ability of the uncrosslinked film layer can be maintained for about 1 year, while the surface charge elimination ability of the crosslinked coating layer can be maintained for about 3 years.

[0029] The beneficial effects of the ionomer coating for eliminating surface charge, its preparation method, and the corresponding coating of the present invention are as follows: (1) It can significantly improve the service life without affecting the storage period and coating performance of acidic ionomer coatings.

[0030] (2) The ionomer coating of the present invention for eliminating surface charge can be cured into a film at low temperature and is suitable for heat-sensitive plastic substrates.

[0031] (3) The ionomer coating of the present invention for eliminating surface charge can be formulated into a water-based coating to reduce pollution.

[0032] (4) The raw materials used in the ionomer coating for eliminating surface charge of the present invention are low in cost, easy to implement, and suitable for large-scale industrial applications. Attached Figure Description

[0033] Figure 1 This is a schematic diagram of a coating structure using ionomers as surface charge eliminators. Detailed Implementation

[0034] To more clearly describe the technical content of the present invention, the following description is provided in conjunction with specific embodiments.

[0035] Example 1 100 g of a 30% aqueous solution of 4-vinylbenzenesulfonic acid homopolymer was mixed thoroughly with 8.56 g of diethanolamine. 700 g of methanol was added for dilution, followed by 10.27 g of melamine, and the mixture was stirred until homogeneous. 170 g of 30% neutralized ASE-60 aqueous polyacrylate was added to the above solution and stirred until dissolved. This solution was coated onto a polytetrafluoroethylene (PTFE) sheet, the solvent was dried at 60°C, and after cooling, the resulting film was peeled off. The resistance of the film was measured; the resistance in the thickness direction for a 0.8 mm thick sheet was 2 × 10⁻⁶. 6 Ohms. When the sample sheet is placed indoors without any encapsulation and exposed to air and light, the resistivity in the thickness direction drops to 9 × 10⁻⁶. 9 Ohm, it will take 3 years.

[0036] Example 2 30 g of acrylic homopolymer was dissolved in 900 g of N,N-dimethylformamide, and then mixed thoroughly with 39.92 g of triethanolamine and 20.04 g of benzomelamine. 0.82 g of E51 bisphenol A epoxy resin was then added and stirred until homogeneous. 10 g of hydroxypropyl cellulose was added to the above solution and stirred until dissolved. This solution was coated onto a polytetrafluoroethylene (PTFE) plate, dried at 85°C for 2 hours, and after cooling, the resulting film was peeled off and its resistance was tested. The resistance of a 0.8 mm thick film in the thickness direction was 5 × 10⁻⁶. 7 Ohms. When the sample sheet is placed indoors without any encapsulation and exposed to air and light, the resistivity in the thickness direction drops to 9 × 10⁻⁶. 9 Ohm, it will take 3 years.

[0037] Example 3 30 g of acrylic homopolymer was dissolved in 900 g of ethanol. 16.19 g of ethyl isonicotinate and 32.43 g of tris(hydroxymethyl)aminomethane were added and mixed thoroughly. 21 g of cellulose acetate was then added to the solution, stirred at 60°C until dissolved, and then cooled. Finally, 0.79 g of F51 bisphenol A type phenolic epoxy resin linear phenolic polyglycidyl ether was added and stirred thoroughly. This solution was coated onto a polytetrafluoroethylene (PTFE) plate, dried at 85°C for 2 hours, and after cooling, the resulting film was peeled off and its resistance was tested. The resistance of a 0.8 mm thick film in the thickness direction was 4 × 10⁻⁶. 7 Ohms. When the sample sheet is placed indoors without any encapsulation and exposed to air and light, the resistivity in the thickness direction drops to 9 × 10⁻⁶. 9 Ohm, it will take 3 years.

[0038] Example 4 30 g of acrylic homopolymer was dissolved in 900 g of ethanol. 16.19 g of ethyl isonicotinate and 32.43 g of trimethylolaminomethane were added and mixed thoroughly. 21 g of cellulose acetate was then added to the above solution, stirred at 60°C until dissolved, and then cooled. Finally, 0.21 g of trimethylolpropane triglycidyl ether and 0.22 g of 3,3'-(oxydimethylene)bis(3-ethyl)oxetane were added and stirred thoroughly. This solution was coated onto a polytetrafluoroethylene (PTFE) plate, dried at 85°C for 2 hours, and after cooling, the resulting film was peeled off and its resistance was tested. The resistance of a 0.8 mm thick film in the thickness direction was 4 × 10⁻⁶. 7 Ohms. When the sample sheet is placed indoors without any encapsulation and exposed to air and light, the resistivity in the thickness direction drops to 9 × 10⁻⁶. 9 Ohm, it will take 3 years.

[0039] Example 5 770 g of ethylene glycol methyl ether was added to dilute 100 g of a 30% polystyrene sulfonic acid aqueous solution. Then, 17.04 g of bis(2-hydroxymethyl)amino-tris(hydroxymethyl)methane, 11.13 g of N,N-dihydroxyethyldodecylamine, and 14.56 g of N,N-dihydroxyethyloctadecylamine were added and mixed thoroughly. 89 g of 30% ASE-60 aqueous polyacrylate was added to the above solution and stirred until dissolved. Then, 0.3 g of diglycidyl phthalate was added and stirred thoroughly. This solution was then coated onto a polytetrafluoroethylene (PTFE) sheet. After drying the solvent at 85°C for 2 hours, the sheet was cooled and the resulting film was peeled off. The resistance of the film was measured; the resistance in the thickness direction for a 0.8 mm thick sheet was 4 × 10⁻⁶. 6 Ohms. When the sample sheet is placed indoors without any encapsulation and exposed to air and light, the resistivity in the thickness direction drops to 9 × 10⁻⁶. 9 Ohm, it will take 3 years.

[0040] Example 6 100 g of a 1.2% aqueous dispersion of the polymer shown in formula (II) (where the mass ratio of the positively charged polymer to the 4-vinylbenzenesulfonic acid homopolymer is 1:2.5) was diluted with 450 g of ethanol and 450 g of dimethyl sulfoxide. Then, 0.16 g of tris(hydroxymethyl)aminomethane and 0.27 g of bis(2-hydroxyethyl)amino-tris(hydroxymethyl)methane were added and thoroughly mixed. 375 g of a copolymer solution of methyl acrylate, ethyl methacrylate, and acrylic acid to methacrylate in a mass ratio of 75:15:5:5 (concentration 20%, solvent: ethanol to dimethyl sulfoxide in a mass ratio of 1:1) was added to the above solution and stirred until homogeneous. Then, 0.24 g of 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylcarboxylate was added, and the solution was stirred until homogeneous. The solution was then coated onto an acrylic glass plate, the solvent was dried at 70°C, and the plate was then heated to 85°C and baked for 2 hours. After cooling, the surface resistivity was measured to be 3 × 10⁻⁶. 6 Ohms. The sample was placed indoors without any encapsulation, exposed to air and light, until the surface resistivity decreased to 9 × 10⁻⁶. 9 Ohm, it will take 3 years.

[0041] Example 7 100 g of a 1.2% aqueous dispersion of the polymer shown in formula (II) (where the mass ratio of the positively charged polymer to the 4-vinylbenzenesulfonic acid homopolymer is 1:2.5) was diluted with 450 g of ethanol and 450 g of dimethyl sulfoxide. Then, 0.23 g of pyridine and 0.07 g of 4-hydroxypyridine were added and thoroughly mixed. 375 g of a copolymer solution of ethyl acrylate, ethyl methacrylate, and acrylic acid to methacrylate in a mass ratio of 70:20:5:5 (concentration 20%, solvent: ethanol to dimethyl sulfoxide mass ratio 1:1) was added to the above solution and stirred until homogeneous. Then, 0.1 g of glycerol triglycidyl ether was added, and the solution was stirred until homogeneous. The solution was then coated onto an acrylic glass plate, the solvent was dried at 70°C, and then the plate was heated to 85°C and baked for 2 hours. After cooling, the surface resistivity was measured to be 2 × 10⁻⁶. 6 Ohms. The sample was placed indoors without any encapsulation, exposed to air and light, until the surface resistivity decreased to 9 × 10⁻⁶. 9 Ohm, it will take 3 years.

[0042] Example 8 100 g of a 1.2% aqueous dispersion of the polymer shown in formula (II) (where the mass ratio of the positively charged polymer to the 4-vinylbenzenesulfonic acid homopolymer is 1:2.5) was diluted with 450 g of ethanol and 450 g of dimethyl sulfoxide. Then, 0.12 g of benzimidazole, 0.13 g of benzotriazole, 0.18 g of N,N-dihydroxyethyldodecylamine, and 0.22 g of N,N-dihydroxyethyloctadecylamine were added and thoroughly mixed. 375 g of a copolymer solution of butyl acrylate, methyl methacrylate, and acrylic acid to methacrylic acid in a mass ratio of 10:80:5:5 (concentration 20%, solvent: ethanol to dimethyl sulfoxide mass ratio 1:1) was added to the above solution and stirred thoroughly. Then, 0.1 g of ethylene glycol diglycidyl ether was added, and the solution was coated onto an acrylic glass plate. The solvent was dried at 70°C, and then the plate was heated to 85°C and baked for 2 hours. After cooling, the surface resistivity was measured to be 2 × 10⁻⁶. 6 Ohms. The sample was placed indoors without any encapsulation, exposed to air and light, until the surface resistivity decreased to 9 × 10⁻⁶. 9 Ohm, it will take 3 years.

[0043] Example 9 100 g of a 1.2% aqueous dispersion of the polymer shown in formula (II) (where the mass ratio of the positively charged polymer to the 4-vinylbenzenesulfonic acid homopolymer is 1:2.5) was diluted with 450 g of propanol and 450 g of dimethyl sulfoxide. Then, 0.11 g of pyridine, 0.08 g of 2-hydroxyethylpyridine, and 0.08 g of 2-hydroxymethylpyridine were added and thoroughly mixed. 500 g of a copolymer solution of methyl acrylate, isobutyl methacrylate, and acrylic acid to methacrylate in a mass ratio of 84:10:3:3 (concentration 15%, solvent: propanol to dimethyl sulfoxide mass ratio 1:1) was added to the above solution and stirred thoroughly. Then, 0.11 g of diglycidyl dimerate was added, and the solution was coated onto an acrylic glass plate. The solvent was dried at 70°C, and then the plate was heated to 85°C and baked for 2 hours. After cooling, the surface resistivity was measured to be 2 × 10⁻⁶. 6 Ohms. The sample was placed indoors without any encapsulation, exposed to air and light, until the surface resistivity decreased to 9 × 10⁻⁶. 9 Ohm, it will take 3 years.

[0044] Example 10 100 g of a 1.2% aqueous dispersion of the polymer shown in formula (II) (where the mass ratio of the positively charged polymer to the 4-vinylbenzenesulfonic acid homopolymer is 1:2.5) was diluted with 450 g of ethanol and 450 g of dimethyl sulfoxide. Then, 0.11 g of pyridine, 0.1 g of 2-hydroxybutylpyridine, and 0.09 g of 3-pyridinepropanol were added and thoroughly mixed. 500 g of a copolymer solution of octadecyl acrylate, methyl methacrylate, and acrylic acid to methacrylic acid in a mass ratio of 10:84:3:3 (concentration 15%, solvent: ethanol to dimethyl sulfoxide in a mass ratio of 1:1) was added to the above solution and stirred thoroughly. Then, 0.11 g of diethylene glycol diglycidyl ether was added, and the solution was coated onto an acrylic glass plate. The solvent was dried at 70°C, and then the plate was heated to 85°C and baked for 2 hours. After cooling, the surface resistivity was measured to be 3 × 10⁻⁶. 6 Ohms. The sample was placed indoors without any encapsulation, exposed to air and light, until the surface resistivity decreased to 9 × 10⁻⁶. 9 Ohm, it will take 3 years.

[0045] Example 11 100 g of a 1.2% aqueous dispersion of the polymer shown in formula (II) (where the mass ratio of the positively charged polymer to the 4-vinylbenzenesulfonic acid homopolymer is 1:2.5) was diluted with 450 g of propanol and 450 g of dimethyl sulfoxide. Then, 0.2 g of pyridine and 0.32 g of octyltriazine ketone were added and thoroughly mixed. 500 g of a copolymer solution of methyl acrylate, isobutyl methacrylate, and acrylic acid to methacrylic acid in a mass ratio of 84:10:3:3 (concentration 15%, solvent: propanol to dimethyl sulfoxide mass ratio 1:1) was added to the above solution and stirred until homogeneous. Then, 0.096 g of 2,4,6-tris(2,4-dihydroxyphenyl)-1,3,5-triazine was added, and the mixture was stirred until homogeneous. The solution was then coated onto an acrylic glass plate, the solvent was dried at 70°C, and after cooling, the surface resistivity was measured to be 2 × 10⁻⁶. 6 Ohms. The sample was placed indoors without any encapsulation, exposed to air and light, until the surface resistivity decreased to 9 × 10⁻⁶. 9 Ohm, it will take 3 years.

[0046] Example 12 100 g of a 1.2% aqueous dispersion of the polymer shown in formula (II) (where the mass ratio of the positively charged polymer to the 4-vinylbenzenesulfonic acid homopolymer is 1:2.5) was diluted with 450 g of propanol and 450 g of dimethyl sulfoxide. Then, 0.15 g of 4-hydroxymethylpyridine, 0.13 g of 4-hydroxypyridine, and 0.096 g of octyltriazine ketone were added and thoroughly mixed. 500 g of a copolymer solution of methyl acrylate, isobutyl methacrylate, and acrylic acid to methacrylic acid in a mass ratio of 89:5:3:3 (concentration 15%, solvent: propanol to dimethyl sulfoxide mass ratio 1:1) was added to the above solution and stirred until homogeneous. Then, 0.096 g of 2,4,6-tris(2,4-dihydroxyphenyl)-1,3,5-triazine was added, and the mixture was stirred until homogeneous. The solution was then coated onto an acrylic glass plate, the solvent was dried at 70°C, and after cooling, the surface resistivity was measured to be 3 × 10⁻⁶. 6 Ohms. The sample was placed indoors without any encapsulation, exposed to air and light, until the surface resistivity decreased to 9 × 10⁻⁶. 9 Ohm, it will take 3 years.

[0047] Example 13 100 g of a 1.2% aqueous dispersion of the polymer shown in formula (II) (where the mass ratio of the positively charged polymer to the 4-vinylbenzenesulfonic acid homopolymer is 1:2.5) was diluted with 450 g of ethanol and 450 g of dimethyl sulfoxide. Then, 0.13 g of 1-hydroxymethylbenzimidazole, 0.12 g of 4-hydroxybenzimidazole, 0.14 g of 2-methyl-5-hydroxybenzimidazole, and 0.096 g of octyltriazine ketone were added and thoroughly mixed. 500 g of a copolymer solution (15% concentration, solvent: ethanol to dimethyl sulfoxide, mass ratio 10:84:3:3) of ethyl acrylate, methyl methacrylate, and acrylic acid to methacrylic acid was added to the above solution and stirred until homogeneous. Add 0.096 g of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, stir well, coat the solution onto an acrylic glass plate, dry the solvent at 70°C, and after cooling, test its surface resistivity to be 2 × 10⁻⁶. 6 Ohms. The sample was placed indoors without any encapsulation, exposed to air and light, until the surface resistivity decreased to 9 × 10⁻⁶. 9 Ohm, it will take 3 years.

[0048] Example 14 100 g of a 1.2% aqueous dispersion of the polymer shown in formula (II) (where the mass ratio of the positively charged polymer to the 4-vinylbenzenesulfonic acid homopolymer is 1:2.5) was diluted with 450 g of propanol and 450 g of dimethyl sulfoxide. Then, 0.33 g of 4-hydroxyethylpyridine, 0.096 g of octyltriazine ketone, and 0.096 g of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine were added and thoroughly mixed. 500 g of a copolymer solution of methyl acrylate, methyl methacrylate, and acrylic acid to methacrylic acid in a mass ratio of 10:84:3:3 (concentration 15%, solvent: propanol to dimethyl sulfoxide mass ratio 1:1) was added to the above solution and stirred until homogeneous. Add 0.25 g of 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexyl carboxylate, 0.36 g of bis((3,4-epoxycyclohexyl)methyl) adipate, and 0.39 g of 1,4-cyclohexanediethanol (3,4-epoxycyclohexane carboxylate). After stirring thoroughly, coat the solution onto an acrylic glass plate, dry the solvent at 70°C, and after cooling, test its surface resistivity to be 3 × 10⁻⁶. 6 Ohms. The sample was placed indoors without any encapsulation, exposed to air and light, until the surface resistivity decreased to 9 × 10⁻⁶. 9 Ohm, it will take 3 years.

[0049] Example 15 100 g of a 1.2% aqueous dispersion of the polymer shown in formula (II) (where the mass ratio of the positively charged polymer to the 4-vinylbenzenesulfonic acid homopolymer is 1:2.5) was diluted with 450 g of ethanol and 450 g of dimethyl sulfoxide. Then, 0.045 g of benzimidazole, 0.22 g of 3-hydroxypyridine, 0.06 g of 2-[2,4-bis(2,4-xylyl)-2-(1,3,5-triazinyl)]5-octoxyphenol and 0.05 g of 2-(4,6-diphenyl-1,3,5-triazin-2)-5-n-hexaneoxyphenol were added and thoroughly mixed. 500 g of a copolymer solution (15% concentration, solvent: ethanol to dimethyl sulfoxide, mass ratio 10:84:3:3) of ethyl acrylate, methyl methacrylate, and acrylic acid to methacrylic acid was added to the above solution and stirred until homogeneous. Add 0.75 g of trimethylolpropane triglycidyl ether, stir well, and then coat the solution onto an acrylic glass plate. Dry the solvent at 70°C, then heat to 85°C and bake for 2 hours. After cooling, test its surface resistivity to be 3 × 10⁻⁶. 6 Ohms. The sample was placed indoors without any encapsulation, exposed to air and light, until the surface resistivity decreased to 9 × 10⁻⁶. 9 Ohm, it will take 3 years.

[0050] Example 16 100 g of a 1.2% aqueous dispersion of the polymer shown in formula (II) (where the mass ratio of the positively charged polymer to the 4-vinylbenzenesulfonic acid homopolymer is 1:2.5) was diluted with 450 g of ethanol and 450 g of dimethyl sulfoxide. Then, 0.045 g of benzimidazole, 0.14 g of 2-(3-pyridyl)ethanol, 0.14 g of 1-(3-pyridyl)ethanol, and 0.11 g of bis-ethylethoxyphenol methoxyphenyl triazine were added and thoroughly mixed. 500 g of a copolymer solution (15% concentration, solvent: ethanol to dimethyl sulfoxide mass ratio 1:1) of ethyl acrylate, methyl methacrylate, and acrylic acid to methacrylic acid in a mass ratio of 10:84:3:3 was added to the above solution and stirred until homogeneous. Add 0.75 g of trimethylolpropane triglycidyl ether, stir well, and then coat the solution onto an acrylic glass plate. Dry the solvent at 70°C, then heat to 85°C and bake for 2 hours. After cooling, test its surface resistivity to be 3 × 10⁻⁶. 6 Ohms. The sample was placed indoors without any encapsulation, exposed to air and light, until the surface resistivity decreased to 9 × 10⁻⁶. 9 Ohm, it will take 3 years.

[0051] Example 17 100 g of a 1.2% aqueous dispersion of the polymer shown in formula (II) (where the mass ratio of the positively charged polymer to the 4-vinylbenzenesulfonic acid homopolymer is 1:2.5) was diluted with 450 g of ethanol and 450 g of dimethyl sulfoxide. Then, 0.045 g of benzimidazole, 0.35 g of 3-pyridinebutanol, and 0.11 g of a mixture of 2-[4-[2-hydroxy-3-tetaneoxypropyl]oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2-[4-[2-hydroxy-3-dodecyloxypropyl]oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine were added and thoroughly mixed. Add 500g of a copolymer solution (15% concentration, solvent: ethanol and dimethyl sulfoxide in a mass ratio of 10:84:3:3) of ethyl acrylate, methyl methacrylate, and acrylic acid to methacrylic acid to the above solution, and stir until homogeneous. Then add 0.75g of trimethylolpropane triglycidyl ether, stir until homogeneous, and coat the solution onto an acrylic glass plate. Dry the solvent at 70°C, then heat to 85°C and bake for 2 hours. After cooling, test the surface resistivity; it is 3×10⁻⁶. 6 Ohms. The sample was placed indoors without any encapsulation, exposed to air and light, until the surface resistivity decreased to 9 × 10⁻⁶. 9 Ohm, it will take 3 years.

[0052] Example 18 100 g of a 1.2% aqueous dispersion of the polymer shown in formula (II) (where the mass ratio of the positively charged polymer to the 4-vinylbenzenesulfonic acid homopolymer is 1:2.5) was diluted with 450 g of ethanol and 450 g of dimethyl sulfoxide. Then, 0.045 g of benzimidazole, 0.63 g of N,N-dihydroxyethyldodecylamine, 0.03 g of 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 0.03 g of 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole, and 0.04 g of 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-benzotriazole were added and thoroughly mixed. Add 500g of a copolymer solution (15% concentration, solvent: ethanol and dimethyl sulfoxide in a mass ratio of 10:84:3:3) of ethyl acrylate, methyl methacrylate, and acrylic acid to methacrylate to the above solution, and stir until homogeneous. Then add 0.15g of diglycidyl hexahydrophthalate, stir until homogeneous, and coat the solution onto an acrylic glass plate. Dry the solvent at 70°C, then heat to 85°C and bake for 2 hours. After cooling, test the surface resistivity to be 3×10⁻⁶. 6 Ohms. The sample was placed indoors without any encapsulation, exposed to air and light, until the surface resistivity decreased to 9 × 10⁻⁶. 9 Ohm, it will take 3 years.

[0053] Example 19 100 g of a 1.2% aqueous dispersion of the polymer shown in formula (II) (where the mass ratio of the positively charged polymer to the 4-vinylbenzenesulfonic acid homopolymer is 1:2.5) was diluted with 450 g of ethanol and 450 g of dimethyl sulfoxide. Then, 0.045 g of benzimidazole, 0.63 g of N,N-dihydroxyethyldodecylamine, 0.03 g of 2-(2′-hydroxy-3′,5′-dipentylphenyl)benzotriazole, 0.03 g of 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole, 0.03 g of 2-(2H-benzotriazole-2-yl)-6-(dodecyl)-4-methylphenol, and 0.02 g of 2-(2'-hydroxy-3',5'-bis(α,α-dimethylbenzyl)phenyl)benzotriazole were added and thoroughly mixed. Add 500g of a copolymer solution (15% concentration, solvent: ethanol and dimethyl sulfoxide in a mass ratio of 10:84:3:3) of ethyl acrylate, methyl methacrylate, and acrylic acid to methacrylate to the above solution, and stir until homogeneous. Then add 0.15g of diglycidyl hexahydrophthalate, stir until homogeneous, and coat the solution onto an acrylic glass plate. Dry the solvent at 70°C, then heat to 85°C and bake for 2 hours. After cooling, test the surface resistivity to be 3×10⁻⁶. 6 Ohms. The sample was placed indoors without any encapsulation, exposed to air and light, until the surface resistivity decreased to 9 × 10⁻⁶. 9 Ohm, it will take 3 years.

[0054] Comparative Example 1 100 g of a 1.2% aqueous dispersion of the polymer shown in formula (II) (where the mass ratio of the positively charged polymer to the 4-vinylbenzenesulfonic acid homopolymer is 1:2.5) was diluted with 450 g of propanol and 450 g of dimethyl sulfoxide. 500 g of a copolymer solution of methyl acrylate, methyl methacrylate, and acrylic acid to methacrylic acid in a mass ratio of 10:84:3:3 (concentration 15%, solvent: propanol to dimethyl sulfoxide in a mass ratio of 1:1) was added to the above solution and stirred until homogeneous. The solution was coated onto an acrylic glass plate, the solvent was dried at 70°C, and after cooling, its surface resistivity was measured to be 1 × 10⁻⁶. 6 Ohms. The sample was placed indoors without any encapsulation, exposed to air and light, until the surface resistivity decreased to 9 × 10⁻⁶. 9 Ohm, it will take 1 year.

[0055] In this specification, the invention has been described with reference to specific embodiments thereof. However, it will be apparent that various modifications and variations can be made without departing from the spirit and scope of the invention. Therefore, this specification is to be considered illustrative rather than restrictive.

Claims

1. An ionomer coating for eliminating surface charge, characterized in that, Includes the following components: Main resin; Acidic ionomers; The main crosslinking agent has both hydrogen-bonding groups and base groups, the functionality of its base groups is 1, the functionality of its hydrogen-bonding groups is ≥1, and it is octyltriazine ketone. The molar ratio of the monofunctional base groups in the crosslinking agent with both hydrogen-bonding groups and base groups to the acidic groups in the acidic ionomer is 0.05 to 1. Polar solvents; The coating can be dried at temperatures below 85°C to form the coating used to eliminate surface charge.

2. The ionomer coating for eliminating surface charge according to claim 1, characterized in that, The acidic ionomer is an acidic ionomer that has been partially neutralized by basic groups.

3. The ionomer coating for eliminating surface charge according to claim 2, characterized in that, The number of moles of the basic groups is less than the number of moles of the acidic groups in the acidic ionomer.

4. The ionomer coating for eliminating surface charge according to any one of claims 1 to 3, characterized in that, The acidic ionomer is poly(4-vinylbenzenesulfonic acid), and the basic group is provided by a polymer with a positively charged repeating unit of the following formula (I), wherein the molar number of positively charged groups in the polymer with the repeating unit of the following formula (I) is less than the molar number of acidic groups in the acidic ionomer. 。 5. The ionomer coating for eliminating surface charge according to claim 1, characterized in that, The ionomer coating further includes an epoxy resin auxiliary crosslinking agent, wherein the epoxy resin has a functionality ≥2; or, the epoxy resin is selected from one or more of the following compounds: Bisphenol A type epoxy resin, bisphenol F type epoxy resin, polyphenol type glycidyl ether epoxy resin, aliphatic glycidyl ether epoxy resin, alicyclic epoxy resin, diglycidyl phthalate, hexahydrophthalic acid diglycidyl ether, epoxidized soybean oil, dimer acid diglycidyl ether, trimethylolpropane triglycidyl ether, glycerol triglycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, 4,5-epoxycyclohexane-1,2-dicarboxylic acid diglycidyl ether, 3,3'-(oxydimethylene)bis(3-ethyl)oxetane, 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexyl carboxylate, bis((3,4-epoxycyclohexyl)methyl)adipate, 1,4-cyclohexanediethanol (3,4-epoxycyclohexane carboxylate); The molar ratio between the epoxy groups in the epoxy resin and the acidic groups in the acidic ionomer is 0 to 0.

1.

6. A method for preparing an ionomer coating for eliminating surface charge according to any one of claims 1 to 5, characterized in that, The preparation method includes: The main resin and acidic ionomer are mixed evenly, and then a main crosslinking agent with both hydrogen bonding groups and base groups is added and dissolved in a polar solvent to obtain the ionomer coating for eliminating surface charge. Alternatively, the preparation method may include adding epoxy resin and dissolving it in a polar solvent.

7. A coating for eliminating surface charge, characterized in that, The ionomer coating for eliminating surface charge according to any one of claims 1 to 5 is applied to a substrate, including a plastic substrate, by means of scraping, spraying, gravure printing or screen printing, and the solvent is dried at a temperature below 85°C to form the coating for eliminating surface charge.

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