CN112724757A - Ionomer coating for eliminating surface charge, preparation method thereof and corresponding coating - Google Patents

Ionomer coating for eliminating surface charge, preparation method thereof and corresponding coating Download PDF

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CN112724757A
CN112724757A CN202011578812.6A CN202011578812A CN112724757A CN 112724757 A CN112724757 A CN 112724757A CN 202011578812 A CN202011578812 A CN 202011578812A CN 112724757 A CN112724757 A CN 112724757A
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徐宁
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
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    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D125/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Coating compositions based on derivatives of such polymers
    • C09D125/18—Homopolymers or copolymers of aromatic monomers containing elements other than carbon and hydrogen
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    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
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    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/062—Copolymers with monomers not covered by C09D133/06
    • C09D133/064—Copolymers with monomers not covered by C09D133/06 containing anhydride, COOH or COOM groups, with M being metal or onium-cation
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    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

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Abstract

The invention relates to an ionomer coating for eliminating surface charges, which comprises the following components: a host 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 more than or equal to 1, epoxy resin can be added as an auxiliary cross-linking agent, and the functionality of the epoxy resin is more 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 surface charges, the preparation method thereof and the corresponding coating have the beneficial effects that: the service life of the acidic ionomer coating 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 plastic substrate which is not heat-resistant; can be prepared into water paint to reduce pollution; the used raw materials have low cost and convenient implementation, and are suitable for large-scale industrial application.

Description

Ionomer coating for eliminating surface charge, preparation method thereof and corresponding coating
Technical Field
The invention relates to the technical field of high polymer materials, in particular to an ionomer coating for eliminating surface charges, a preparation method thereof and a corresponding coating.
Background
Ionomers are polymers of monomers having ionic bonds, and mainly include polymers having carboxyl groups or polymers having sulfonic acid groups. It has certain charge transfer capacity, can be blended in insulating polymer paint to endow the paint with charge conduction capacity, and eliminates the charge accumulated on the surface of the coating due to friction, as shown in figure 1.
The acidic ionomer can be dissolved in water or alcohol, and can be blended with a water-soluble coating or an alcohol-soluble coating to form a coating with good dispersibility and high transparency. Compared with graphite or metal powder, the ionomer has better solubility and dispersion stability, and a coating film is colorless and transparent and is suitable for large-scale industrial application. The acidic ionomer may be partially neutralized with the addition of small amounts of basic compounds to adjust properties, including: alkali metal, amino, quaternary ammonium base, pyridine derivative, triazine, 2,4, 6-triphenyl-1, 3, 5-triazine, imidazole, benzimidazole, benzotriazole, oxazole, and a polymer having a positive charge and a repeating unit of the following formula (I).
Figure BDA0002863880340000011
The basic compounds can be used alone or in combination. The number of moles of basic groups < the number of moles of acidic groups on the ionomer.
The organic amine and the alkaline aromatic heterocycle can increase the solubility of the acidic ionomer in alcohol solvent and the compatibility with the coating. The basic compound may be, in addition to small molecules, a conjugated polymer having a positive charge, such as the polymer of the above formula (I), which has a positive charge dispersed over a plurality of conjugated units, and a 4-vinylbenzenesulfonic acid homopolymer partially neutralized with the same, the charge conductivity of which is greatly improved, as shown in the following formula (II).
Figure BDA0002863880340000021
Such polymers can be incorporated into coatings in much smaller amounts (less than 10%) to achieve surface charge dissipation.
However, the acidic ionomers have inherent defects, and ionic groups thereon are dissociated after absorbing moisture, so that the acidic ionomers are separated from each other by the creeping of molecular chains due to mutual repulsion of like charges, thereby generating micro-cracks in the coating film, and the coating film becomes transparent and white. The microcracks block the charge transfer channels, so that the charge eliminating capacity of the coating is quickly reduced, and the service life of the coating is obviously shorter than that of a normal coating. The lower the content of acidic ionomer in the coating, the faster the charge transport capacity decays, the service life generally not exceeding one year and the performance not meeting the industrial requirements. Extending the service life of acidic ionomers requires overcoming the problem of internal cracking of the coating.
To improve the tendency of acidic ionomer coating films to crack, it is common to add crosslinkers, such as: epoxy resins, isocyanates, melamine formaldehyde resins, polyfunctional bases, and the like. However, crosslinking agents which are too reactive at room temperature (e.g.isocyanates or polyfunctional bases) lead to coatings which gel and have too short a pot life to be suitable. Most of the cross-linking agents (such as latent isocyanate, melamine formaldehyde resin and epoxy resin) and the acidic groups need to react at 130-150 ℃, exceed the glass transition temperature of common plastic substrates, and cannot be used on the plastic substrates. Some patents (CN103348520A) deal with this by increasing the ionomer molecular weight and increasing the entanglement. However, the viscosity of the polymer having an excessively high molecular weight is too high, the solubility is lowered, and uniform coating is difficult. The coating requires the use of polymers having a broad molecular weight distribution, and small molecular weight polymers are necessary, so that the method has a limited effect on improving the microcracks of the coating film.
Therefore, there is no ideal proposal which can eliminate the microcracks of the coating film, prolong the service life, can be cured at low temperature and is suitable for the coating film of the plastic substrate.
Disclosure of Invention
Aiming at the technical problems that the acid ionomer coating film is easy to generate microcracks and short in service life, the invention provides an ionomer coating which can effectively prolong the service life and can be cured at low temperature to form a film on a plastic substrate and is used for eliminating surface charges, a preparation method thereof and a corresponding coating.
In order to achieve the above purpose, the technical scheme of the ionomer coating for eliminating the surface charge provided by the invention is as follows:
comprises the following components:
a host 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 more than or equal to 1, epoxy resin can be added as an auxiliary cross-linking agent, and the functionality of the epoxy resin is more than or equal to 2;
a polar solvent.
Preferably, the main resin can be selected from general-purpose insulating coating materials, such as aqueous polyacrylate or aqueous polyurethane. The acidic ionomer may be compatible with many water-soluble or alcohol-soluble resins, such as polyacrylates, polyurethanes, celluloses, polyvinyl acetals. Preferred are polyacrylates with partial carboxyl groups, polyurethanes with partial carboxyl groups, polyvinyl butyrals, cellulose.
Preferably, the acidic ionomer is a pure acidic ionomer or an acidic ionomer partially neutralized with basic groups.
Preferably, the acidic ionomer is selected from one or more of homopolymers or copolymers formed from the following monomers:
acrylic acid, maleic acid, 4-vinylbenzenesulfonic acid, vinylsulfonic acid,
namely, it may be: acrylic acid homopolymers, copolymers of acrylic acid with other monomers, copolymers of maleic acid with other monomers, 4-vinylbenzenesulfonic acid homopolymers, copolymers of 4-vinylbenzenesulfonic acid with other monomers, vinylsulfonic acid homopolymers, and copolymers of vinylsulfonic acid with other monomers.
Preferably, the basic group is provided by one or more of the following basic compounds:
alkali metal, amino, quaternary ammonium base, pyridine derivative, triazine, 2,4, 6-triphenyl-1, 3, 5-triazine, imidazole, benzimidazole, benzotriazole, oxazole, and a polymer having a repeating unit of the following formula (I) having a positive charge
Figure BDA0002863880340000031
The number of moles of basic groups is less than the number of moles of acidic groups in the acidic ionomer.
Preferably, the acidic ionomer is poly-4-vinylbenzenesulfonic acid, the basic groups are provided by a polymer having a positive charge and repeating units of formula (I),
Figure BDA0002863880340000032
the number of moles of positively charged groups in the polymer of formula (I) is < the number of moles of acidic groups in the acidic ionomer.
Preferably, the crosslinking agent having both hydrogen bonding groups and base groups is selected from one or more of the following compounds:
amines containing a carbon hydroxyl group, pyridines containing a carbon hydroxyl group, imidazoles containing a carbon hydroxyl group, benzimidazoles containing a carbon hydroxyl group, benzotriazoles containing a carbon hydroxyl group, melamines containing a carbon hydroxyl group, 2,4, 6-triphenyl-1, 3-5-triazine containing a carbon hydroxyl group;
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 hydroxy-substituted 2,4, 6-triphenyl-1, 3-5-triazine derivatives, diethanolamine, triethanolamine, tris (hydroxymethyl) aminomethane, bis (2-hydroxymethyl) amino-tris (hydroxymethyl) methane, N-dihydroxyethyldodecylamine, N-dihydroxyethyloctadecylamine, 2-hydroxymethylpyridine, 2-hydroxyethylpyridine, 2-pyridylpropanol, 2-pyridylbutanol, 3-hydroxypyridine, 3-hydroxymethylpyridine, 2- (3-pyridyl) ethanol, 1- (3-pyridyl) ethanol, 3-pyridylpropanol, 3-pyridylbutanol, 4-hydroxypyridine, 4-triphenylamine, 2, 4-triphenylamine, 3-triazine derivatives, diethanolamine, triethanolamine, tris (hydroxymethyl) methane, N-dihydroxyethyldodecylamine, N-dihydroxyethyloctadecylamine, 4-hydroxymethylpyridine, 4-hydroxyethylpyridine, 4-pyridylpropanol, 4-pyridinebutanol, 1- (2-hydroxyethyl) imidazole, 1-hydroxymethylbenzimidazole, 4-hydroxybenzimidazole, 2-methyl-5-hydroxybenzimidazole, melamine, benzoguanamine, 2- (2 '-hydroxy-3' -tert-butyl-5 '-methylphenyl) -5-chlorobenzotriazole, 2- (2' -hydroxy-3 ',5' -di-tert-butylphenyl) -benzotriazole, 2- (2 '-hydroxy-3', 5 '-dipentylphenyl) benzotriazole, 2- (2' -hydroxy-5 '-tert-octylphenyl) benzotriazole, 2- (2' -hydroxy-3 ',5' -bis (. alpha.,. alpha. -dimethylbenzyl) phenyl) benzotriazole, 2- (2H-benzotriazol-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-bis (2, 4-dimethylphenyl) -1,3, 5-triazine, 2- [2, 4-bis (2, 4-xylyl) -2- (1,3, 5-triazinyl) ] 5-octyloxyphenol, octyltriazone, 2- (4, 6-diphenyl-1, 3, 5-triazine-2) -5-n-hexylalkoxyphenol, bis-ethylethoxyphenol methoxyphenyl triazine, 2- [4- [ 2-hydroxy-3-tridecyloxypropyl ] 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 mixture;
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-dihydroxyethyldodecylamine, N-dihydroxyethyloctadecylamine, 2-hydroxymethylpyridine, 2-hydroxyethylpyridine, 2-pyridinylpropanol, 2-pyridinylbutanol, 3-hydroxypyridine, 3-hydroxymethylpyridine, 2- (3-pyridyl) ethanol, 1- (3-pyridyl) ethanol, 3-pyridinylpropanol, 3-pyridinylbutanol, 4-hydroxypyridine, 4-hydroxymethylpyridine, 4-hydroxyethylpyridine, 4-pyridinylpropanol, 4-pyridinylbutanol, 1-hydroxymethylbenzimidazole, 4-hydroxybenzimidazole, 2-methyl-5-hydroxybenzimidazole, melamine, benzoguanamine, 2- (2 '-hydroxy-3' -tert-butyl-5 '-methylphenyl) -5-chlorobenzotriazole, 2- (2' -hydroxy-3 ',5' -di-tert-butylphenyl) -benzotriazole, 2- (2 '-hydroxy-3', 5 '-dipentylphenyl) benzotriazole, 2- (2' -hydroxy-5 '-tert-octylphenyl) benzotriazole, 2- (2' -hydroxy-3 ',5' -bis (. alpha.,. alpha. -dimethylbenzyl) phenyl) benzotriazole, 2- (2H-benzotriazol-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-bis (2, 4-dimethylphenyl) -1,3, 5-triazine, 2- [2, 4-bis (2, 4-dimethylphenyl) -2- (1,3, 5-triazinyl) ] 5-octyloxyphenol, octyltriazone, 2- (4, 6-diphenyl-1, 3, 5-triazine-2) -5-n-hexylalkoxyphenol, bis-ethylethoxyphenol methoxyphenyl triazine, bis-ethylethoxyphenyl triazine, 2- [4- [ 2-hydroxy-3-tridecyloxypropyl ] 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 mixtures.
The molar ratio of the monofunctional basic group in the crosslinking agent with the hydrogen bond group and the basic group to the acidic group in the acidic ionomer is 0.05-1.
Preferably, the ionomer coating for eliminating surface charges can also be added with epoxy resin as an auxiliary crosslinking agent, and the functionality of the epoxy group is more than or equal to 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, diglycidyl hexahydrophthalate, epoxidized soybean oil, dimer acid diglycidyl ester, trimethylolpropane triglycidyl ether, glycerol triglycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, 4, 5-epoxycyclohexane-1, 2-dicarboxylic acid diglycidyl ester, 3' - (oxybis-methylene) bis (3-ethyl) oxetane, 3, 4-epoxycyclohexylmethyl 3, 4-epoxycyclohexyl formate, bis ((3, 4-epoxycyclohexyl) methyl) adipate, 1, 4-cyclohexanedimethanol (3, 4-epoxycyclohexanecarboxylic acid) ester;
preferably, the molar ratio of the epoxy group in the epoxy resin to the acidic group in the acidic ionomer is 0 to 0.1.
In the ionomer coating for removing surface charges of the present invention, a primary crosslinking agent having both a hydrogen bond group and a monofunctional base is used to stabilize an acid group and to offset repulsive force between anions on an ionomer by pulling force of an ionic bond and a hydrogen bond. Specifically, first, basic groups and hydrogen bonding groups can stabilize acidic groups on the ionomer. The acidic groups (such as sulfonic acid) have certain oxidability and are unstable, the film is easy to yellow and discolor after being formed, the performance is reduced, the stability of the acid groups and basic groups after being neutralized and salified can be greatly improved, hydrogen bond groups (such as hydroxyl) also have a stabilizing effect on the acidic groups, and the service life of the ionomer can be effectively prolonged. Secondly, the basic group and the acid group can be directly combined by an ionic bond, and a hydrogen bond group (such as a hydroxyl group, a phenol group and a nitrogen-hydrogen group) can be combined with the acid group by the hydrogen bond, so that the repulsive force between anions on the ionomer can be counteracted by the tensile force of the ionic bond and the hydrogen bond, and the tendency of forming microcracks in the coating film can be overcome. The ionic bond is a strong binding force, and if the functionality exceeds 1, a gel phenomenon is caused, while the hydrogen bond is weak, and no gel is generated by increasing the functionality. The two crosslinking actions can be achieved at room temperature without causing a gel phenomenon, the crosslinking agent and the acidic ionomer can be co-dissolved in a solvent, the fluidity and the good coating performance are kept, the coating is dried at low temperature after coating to form a crosslinked coating, the drying temperature is between room temperature and 85 ℃, the service life is prolonged, the low-temperature curing condition is met, and the coating is suitable for plastic substrate coating.
On the basis of adding the main cross-linking agent which has both hydrogen bond groups and single functionality basic groups, a small amount of epoxy resin can be added for auxiliary cross-linking, so that microcracks generated in the film layer are eliminated. In general, bases of tertiary amines, imidazoles, benzimidazoles, pyridines and quaternary ammonium salts thereof have a catalytic effect on the ring-opening crosslinking reaction of epoxy resins with carboxyl groups, and the reaction temperature of epoxy resins with carboxyl groups on acidic ionomers is above 120 ℃ in the absence of a catalyst, and can be carried out at a lower temperature in the presence of a catalyst. The crosslinking agent with both hydrogen bond groups and single-functionality basic groups comprises structures such as tertiary amine, imidazole, benzimidazole, pyridine and the like, and experiments show that the benzotriazole, melamine and 2,4, 6-triphenyl-1, 3-5-triazine structures contained in the crosslinking agent with both hydrogen bond groups and basic groups can also catalyze the reaction of ring opening and carboxyl of epoxy resin. Therefore, when the main crosslinking agent having both hydrogen bond groups and monofunctional bases exists, the epoxy resin can participate in the reaction as an auxiliary crosslinking agent, is cured at low temperature to form a film, is suitable for coating on a plastic substrate, and can be selectively added according to actual needs.
In the ionomer coating for removing surface charges of the present invention, if necessary, an auxiliary agent such as a thickener, an antioxidant, an anti-scratch agent, etc. may be further added.
The present invention also provides a method for preparing the ionomer coating for removing surface charges according to the claims, comprising:
uniformly mixing the main resin and the acidic ionomer, and then adding a main cross-linking agent with hydrogen bond groups and basic groups to dissolve in a polar solvent to obtain the ionomer coating for eliminating surface charges;
preferably, the preparation method comprises adding the epoxy resin and dissolving in the polar solvent.
The polar solvent may be water, alcohols, N-dimethylformamide, or dimethyl sulfoxide, etc.
The invention also provides a coating for eliminating the surface charge, the ionomer coating for eliminating the surface charge is coated on a base material including a plastic substrate in a blade coating, curtain coating, gravure printing or screen printing mode, and a solvent is dried to form the coating for eliminating the surface charge.
The curing film-forming temperature of the coating is between room temperature and 85 ℃, for example, between 20 and 85 ℃, and the coating is suitable for coating of flexible plastic substrates which cannot resist high temperature.
The volume resistance or surface resistance of the coating is 106Ohm-109Between ohms. The paint using water-based polyacrylate or water-based polyurethane as main resin has the surface charge eliminating capacity of the uncrosslinked film layer maintained for about 1 year, and the surface charge eliminating capacity of the crosslinked coating maintained for about 3 years.
The ionomer coating for eliminating surface charges, the preparation method thereof and the corresponding coating have the beneficial effects that:
(1) the service life of the acidic ionomer coating can be greatly prolonged on the premise of not influencing the storage life and the coating performance of the acidic ionomer coating.
(2) The ionomer coating for eliminating surface charges can be cured at low temperature to form a film, and is suitable for thermolabile plastic substrates.
(3) The ionomer coating for eliminating surface charges can be prepared into a water-based coating, so that pollution is reduced.
(4) The ionomer coating for eliminating surface charges has the advantages of low cost of raw materials, convenient implementation and suitability for large-scale industrial application.
Drawings
FIG. 1 is a schematic view of a coating structure using an ionomer as a surface charge eliminator.
Detailed Description
In order to more clearly describe the technical contents of the present invention, the following further description is given in conjunction with specific embodiments.
Example 1
30% of100 g of 4-vinyl benzenesulfonic acid homopolymer aqueous solution and 8.56 g of diethanolamine are uniformly mixed, 700 g of methanol is added to dilute the mixture, 10.27 g of melamine is added to the mixture, and the mixture is uniformly stirred. 170 g of 30% neutralized ASE-60 aqueous polyacrylate was added to the above solution and dissolved by stirring. Coating the solution on a polytetrafluoroethylene plate, drying the solvent at 60 deg.C, cooling, removing the formed film, testing the resistance, wherein the resistance of 0.8 mm thick sheet in the thickness direction is 2 × 106Ohm. The sample piece was placed in a room without any encapsulation, and was exposed to air and light, and the resistance in the thickness direction was lowered to 9X 109Ohm, 3 years.
Example 2
30 g of acrylic homopolymer is dissolved in 900 g of N, N-dimethylformamide, 39.92 g of triethanolamine and 20.04 g of benzoguanamine are mixed uniformly, and then 0.82 g of E51 bisphenol A epoxy resin is added and stirred uniformly. To the above solution, 10 g of hydroxypropyl cellulose was added and dissolved with stirring. Coating the solution on a polytetrafluoroethylene plate, drying the solvent at 85 deg.C, maintaining for 2 hr, cooling, removing the formed film, and testing the resistance of the film, wherein the resistance of the 0.8 mm thick sheet in the thickness direction is 5 × 107Ohm. The sample piece was placed in a room without any encapsulation, and was exposed to air and light, and the resistance in the thickness direction was lowered to 9X 109Ohm, 3 years.
Example 3
30 g of acrylic acid homopolymer are dissolved in 900 g of ethanol, 16.19 g of ethyl isonicotinate and 32.43 g of tris (hydroxymethyl) aminomethane are added and mixed uniformly. To the above solution was added 21 g of cellulose acetate, dissolved with stirring at 60 ℃ and cooled. Finally, 0.79 g of F51 bisphenol A type novolac epoxy resin polyglycidyl ether is added and stirred uniformly. Coating the solution on a polytetrafluoroethylene plate, drying the solvent at 85 deg.C, maintaining for 2 hr, cooling, removing the formed film, and testing the resistance of the sheet with thickness of 0.8 mm to 4 × 107Ohm. The sample piece was placed in a room without any encapsulation, and was exposed to air and light, and the resistance in the thickness direction was lowered to 9X 109Ohm, 3 years.
Example 4
30 g of acrylic acid homopolymer are dissolved in 900 g of ethanol, 16.19 g of ethyl isonicotinate and 32.43 g of tris (hydroxymethyl) aminomethane are added and mixed uniformly. To the above solution was added 21 g of cellulose acetate, dissolved with stirring at 60 ℃ and cooled. Finally, 0.21 g of trimethylolpropane triglycidyl ether and 0.22 g of 3, 3' - (oxybis-methylene) bis (3-ethyl) oxetane were added and stirred well. Coating the solution on a polytetrafluoroethylene plate, drying the solvent at 85 deg.C, maintaining for 2 hr, cooling, removing the formed film, and testing the resistance of the sheet with thickness of 0.8 mm to 4 × 107Ohm. The sample piece was placed in a room without any encapsulation, and was exposed to air and light, and the resistance in the thickness direction was lowered to 9X 109Ohm, 3 years.
Example 5
770 g of ethylene glycol monomethyl ether was added to 100 g of a 30% aqueous solution of polystyrenesulfonic acid to dilute the solution. 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 well. 89 g of 30% ASE-60 aqueous polyacrylate was added to the above solution, and dissolved by stirring. Adding 0.3 g of diglycidyl phthalate, stirring, coating the solution on a polytetrafluoroethylene plate, drying the solvent at 85 ℃, keeping for 2 hours, cooling, removing the formed film, and testing the resistance, wherein the resistance of a 0.8 mm thick sheet in the thickness direction is 4 multiplied by 106Ohm. The sample piece was placed in a room without any encapsulation, and was exposed to air and light, and the resistance in the thickness direction was lowered to 9X 109Ohm, 3 years.
Example 6
To 100 g of a 1.2% strength aqueous dispersion of a polymer represented by the formula (II) (wherein the mass ratio of the positively charged polymer to the 4-vinylbenzenesulfonic acid homopolymer was 1:2.5), 450 g of ethanol and 450 g of dimethyl sulfoxide were added to dilute the dispersion. Then 0.16 g of tris (hydroxymethyl) aminomethane and 0.27 g of bis (2-hydroxyethyl) amino-tris (hydroxymethyl) methane were added and mixed well. Adding methyl acrylate and methacrylic acid into the solution375 g of copolymer solution (the concentration is 20 percent, and the solvent is ethanol and dimethyl sulfoxide in a mass ratio of 1:1) with the mass ratio of ethyl ester, acrylic acid and methacrylic acid being 75:15:5:5, and the mixture is stirred uniformly. Adding 0.24 g of 3, 4-epoxy cyclohexyl methyl 3, 4-epoxy cyclohexyl formic ether, stirring uniformly, coating the solution on an organic glass plate, drying the solvent at 70 ℃, heating to 85 ℃, baking for 2 hours, cooling and testing the surface resistance to be 3 multiplied by 106Ohm. Placing the sample piece in a room without packaging, contacting with air and light, and lowering the surface resistance to 9 × 109Ohm, 3 years.
Example 7
To 100 g of a 1.2% strength aqueous dispersion of a polymer represented by the formula (II) (wherein the mass ratio of the positively charged polymer to the 4-vinylbenzenesulfonic acid homopolymer was 1:2.5), 450 g of ethanol and 450 g of dimethyl sulfoxide were added to dilute the dispersion. Then 0.23 g of pyridine and 0.07 g of 4-hydroxypyridine are added and mixed well. 375 g (20% concentration, 1:1 mass ratio of ethanol to dimethyl sulfoxide) of ethyl acrylate, ethyl methacrylate, and copolymer solution of acrylic acid and methacrylic acid at a mass ratio of 70:20:5:5 are added into the solution, and the mixture is stirred uniformly. Adding 0.1 g of glycerol triglycidyl ether, stirring, coating the solution on an organic glass plate, drying the solvent at 70 ℃, heating to 85 ℃, baking for 2 hours, cooling and testing the surface resistance to be 2 multiplied by 106Ohm. Placing the sample piece in a room without packaging, contacting with air and light, and lowering the surface resistance to 9 × 109Ohm, 3 years.
Example 8
To 100 g of a 1.2% strength aqueous dispersion of a polymer represented by the formula (II) (wherein the mass ratio of the positively charged polymer to the 4-vinylbenzenesulfonic acid homopolymer was 1:2.5), 450 g of ethanol and 450 g of dimethyl sulfoxide were added to dilute the dispersion. 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 mixed well. 375 g of a copolymer solution of butyl acrylate, methyl methacrylate and acrylic acid and methacrylic acid with the mass ratio of 10:80:5:5 is added into the solution(the concentration is 20%, the solvent is ethanol and dimethyl sulfoxide in a mass ratio of 1:1), and stirring uniformly. Adding 0.1 g of ethylene glycol diglycidyl ether, stirring, coating the solution on an organic glass plate, drying the solvent at 70 ℃, heating to 85 ℃, baking for 2 hours, cooling, and testing the surface resistance to be 2 multiplied by 106Ohm. Placing the sample piece in a room without packaging, contacting with air and light, and lowering the surface resistance to 9 × 109Ohm, 3 years.
Example 9
To 100 g of a 1.2% strength aqueous dispersion of a polymer of the formula (II) in which the mass ratio of the positively charged polymer to the 4-vinylbenzenesulfonic acid homopolymer was 1:2.5, 450 g of propanol and 450 g of dimethyl sulfoxide were added for dilution. Then 0.11 g of pyridine, 0.08 g of 2-hydroxyethyl pyridine and 0.08 g of 2-hydroxymethyl pyridine are added and mixed fully and evenly. To the above solution, 500 g (concentration 15%, solvent is propanol to dimethyl sulfoxide mass ratio 1:1) of methyl acrylate, isobutyl methacrylate, and copolymer solution of acrylic acid to methacrylic acid mass ratio 84:10:3:3 was added, and stirred uniformly. Adding 0.11 g of dimer acid diglycidyl ester, stirring, coating the solution on an organic glass plate, drying the solvent at 70 ℃, heating to 85 ℃, baking for 2 hours, cooling, and testing the surface resistance to be 2 multiplied by 106Ohm. Placing the sample piece in a room without packaging, contacting with air and light, and lowering the surface resistance to 9 × 109Ohm, 3 years.
Example 10
To 100 g of a 1.2% strength aqueous dispersion of a polymer represented by the formula (II) (wherein the mass ratio of the positively charged polymer to the 4-vinylbenzenesulfonic acid homopolymer was 1:2.5), 450 g of ethanol and 450 g of dimethyl sulfoxide were added to dilute the dispersion. Then 0.11 g of pyridine, 0.1 g of 2-hydroxybutyl pyridine and 0.09 g of 3-pyridylpropanol are added and mixed well. To the above solution, 500 g (concentration 15%, solvent is ethanol to dimethyl sulfoxide mass ratio 1:1) of octadecyl acrylate, methyl methacrylate, and copolymer solution of acrylic acid and methacrylic acid in a mass ratio of 10:84:3:3 was added, and stirred uniformly. 0.11 g of diethylene glycol diglycidyl ether was added,uniformly stirring, coating the solution on organic glass plate, drying the solvent at 70 deg.C, heating to 85 deg.C, baking for 2 hr, cooling, and testing the surface resistance to 3 × 106Ohm. Placing the sample piece in a room without packaging, contacting with air and light, and lowering the surface resistance to 9 × 109Ohm, 3 years.
Example 11
To 100 g of a 1.2% strength aqueous dispersion of a polymer of the formula (II) in which the mass ratio of the positively charged polymer to the 4-vinylbenzenesulfonic acid homopolymer was 1:2.5, 450 g of propanol and 450 g of dimethyl sulfoxide were added for dilution. Then 0.2 g of pyridine and 0.32 g of octyl triazone are added and mixed well. To the above solution, 500 g (concentration 15%, solvent is propanol to dimethyl sulfoxide mass ratio 1:1) of methyl acrylate, isobutyl methacrylate, and copolymer solution of acrylic acid to methacrylic acid mass ratio 84:10:3:3 was added, and stirred uniformly. Then 0.096 g of 2,4, 6-tri (2, 4-dihydroxyphenyl) -1,3, 5-triazine is added, after the solution is evenly stirred, the organic glass plate is coated with the solution, the solvent is dried at 70 ℃, and after the solution is cooled, the surface resistance of the organic glass plate is tested to be 2 multiplied by 106Ohm. Placing the sample piece in a room without packaging, contacting with air and light, and lowering the surface resistance to 9 × 109Ohm, 3 years.
Example 12
To 100 g of a 1.2% strength aqueous dispersion of a polymer of the formula (II) in which the mass ratio of the positively charged polymer to the 4-vinylbenzenesulfonic acid homopolymer was 1:2.5, 450 g of propanol and 450 g of dimethyl sulfoxide were added for dilution. Then 0.15 g of 4-hydroxymethylpyridine, 0.13 g of 4-hydroxypyridine and 0.096 g of octyl triazone were added and mixed well. To the above solution, 500 g (concentration 15%, solvent is propanol to dimethyl sulfoxide mass ratio 1:1) of methyl acrylate, isobutyl methacrylate, and copolymer solution of acrylic acid to methacrylic acid in a mass ratio of 89:5:3:3 were added, and stirred uniformly. Then 0.096 g of 2,4, 6-tri (2, 4-dihydroxyphenyl) -1,3, 5-triazine is added, after the solution is evenly stirred, the organic glass plate is coated with the solution, the solvent is dried at 70 ℃, and after the solution is cooled, the surface resistance of the organic glass plate is tested to be 3 multiplied by 106Ohm. Placing the sample piecePlacing in room, contacting air and light without packaging, and waiting for surface resistance to decrease to 9 × 109Ohm, 3 years.
Example 13
To 100 g of a 1.2% strength aqueous dispersion of a polymer represented by the formula (II) (wherein the mass ratio of the positively charged polymer to the 4-vinylbenzenesulfonic acid homopolymer was 1:2.5), 450 g of ethanol and 450 g of dimethyl sulfoxide were added to dilute the dispersion. 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 octyl triazone were added thereto and mixed well. To the above solution, 500 g (concentration 15%, solvent is ethanol to dimethyl sulfoxide mass ratio 1:1) of ethyl acrylate, methyl methacrylate, and copolymer solution of acrylic acid and methacrylic acid in a mass ratio of 10:84:3:3 was added, and stirred uniformly. Then 0.096 g of 2- (2, 4-dihydroxyphenyl) -4, 6-bis (2, 4-dimethylphenyl) -1,3, 5-triazine is added, the solution is evenly stirred and then coated on an organic glass plate, the solvent is dried at 70 ℃, and the surface resistance of the organic glass plate is tested to be 2 multiplied by 10 after cooling6Ohm. Placing the sample piece in a room without packaging, contacting with air and light, and lowering the surface resistance to 9 × 109Ohm, 3 years.
Example 14
To 100 g of a 1.2% strength aqueous dispersion of a polymer of the formula (II) in which the mass ratio of the positively charged polymer to the 4-vinylbenzenesulfonic acid homopolymer was 1:2.5, 450 g of propanol and 450 g of dimethyl sulfoxide were added for dilution. Then, 0.33 g of 4-hydroxyethylpyridine, 0.096 g of octyl triazone and 0.096 g of 2- (2, 4-dihydroxyphenyl) -4, 6-bis (2, 4-dimethylphenyl) -1,3, 5-triazine were added thereto and mixed well. To the above solution, 500 g (concentration 15%, solvent is propanol to dimethyl sulfoxide mass ratio 1:1) of methyl acrylate, methyl methacrylate, and copolymer solution of acrylic acid to methacrylic acid in a mass ratio of 10:84:3:3 was added, and stirred uniformly. Then, 0.25 g of 3, 4-epoxycyclohexylmethyl 3, 4-epoxycyclohexylformate, 0.36 g of bis ((3, 4-epoxycyclohexyl) methyl) adipate and 0.39 g of 1, 4-cyclohexanedimethanol (3, 4-epoxycyclohexanecarboxylate) were added thereto, and the mixture was stirred well and then coated on organic glassDrying the solvent on a plate at 70 ℃, and testing the surface resistance of the plate to be 3 multiplied by 10 after cooling6Ohm. Placing the sample piece in a room without packaging, contacting with air and light, and lowering the surface resistance to 9 × 109Ohm, 3 years.
Example 15
To 100 g of a 1.2% strength aqueous dispersion of a polymer represented by the formula (II) (wherein the mass ratio of the positively charged polymer to the 4-vinylbenzenesulfonic acid homopolymer was 1:2.5), 450 g of ethanol and 450 g of dimethyl sulfoxide were added to dilute the dispersion. Then, 0.045 g of benzimidazole, 0.22 g of 3-hydroxypyridine and 0.06 g of 2- [2, 4-bis (2, 4-xylyl) -2- (1,3, 5-triazinyl) were added]5-octyloxyphenol and 0.05 g of 2- (4, 6-diphenyl-1, 3, 5-triazine-2) -5-n-hexyloxyphenol were thoroughly mixed. To the above solution, 500 g (concentration 15%, solvent is ethanol to dimethyl sulfoxide mass ratio 1:1) of ethyl acrylate, methyl methacrylate, and copolymer solution of acrylic acid and methacrylic acid in a mass ratio of 10:84:3:3 was added, and stirred uniformly. Adding 0.75 g of trimethylolpropane triglycidyl ether, stirring, coating the solution on an organic glass plate, drying the solvent at 70 ℃, heating to 85 ℃, baking for 2 hours, cooling and testing the surface resistance to be 3 multiplied by 106Ohm. Placing the sample piece in a room without packaging, contacting with air and light, and lowering the surface resistance to 9 × 109Ohm, 3 years.
Example 16
To 100 g of a 1.2% strength aqueous dispersion of a polymer represented by the formula (II) (wherein the mass ratio of the positively charged polymer to the 4-vinylbenzenesulfonic acid homopolymer was 1:2.5), 450 g of ethanol and 450 g of dimethyl sulfoxide were added to dilute the dispersion. 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-ethyl ethoxy phenol methoxyphenyl triazine are added and mixed fully and evenly. To the above solution, 500 g (concentration 15%, solvent is ethanol to dimethyl sulfoxide mass ratio 1:1) of ethyl acrylate, methyl methacrylate, and copolymer solution of acrylic acid and methacrylic acid in a mass ratio of 10:84:3:3 was added, and stirred uniformly. Then 0.75 g of trimethylolpropane triglycidyl ether is added and stirredSpreading the solution on organic glass plate, drying at 70 deg.C, heating to 85 deg.C, baking for 2 hr, cooling, and testing surface resistance to 3 × 106Ohm. Placing the sample piece in a room without packaging, contacting with air and light, and lowering the surface resistance to 9 × 109Ohm, 3 years.
Example 17
To 100 g of a 1.2% strength aqueous dispersion of a polymer represented by the formula (II) (wherein the mass ratio of the positively charged polymer to the 4-vinylbenzenesulfonic acid homopolymer was 1:2.5), 450 g of ethanol and 450 g of dimethyl sulfoxide were added to dilute the dispersion. 0.045 g of benzimidazole, 0.35 g of 3-pyridinebutanol and 0.11 g of 2- [4- [ 2-hydroxy-3-tridecyloxypropyl ] are then added]Oxy radical]-2-hydroxyphenyl]-4, 6-bis (2, 4-dimethylphenyl) -1,3, 5-triazine with 2- [4- [ 2-hydroxy-3-dodecyloxypropyl]Oxy radical]-2-hydroxyphenyl]The mixture of the (E) -4, 6-bis (2, 4-dimethylphenyl) -1,3, 5-triazine is fully and uniformly mixed. To the above solution, 500 g (concentration 15%, solvent is ethanol to dimethyl sulfoxide mass ratio 1:1) of ethyl acrylate, methyl methacrylate, and copolymer solution of acrylic acid and methacrylic acid in a mass ratio of 10:84:3:3 was added, and stirred uniformly. Adding 0.75 g of trimethylolpropane triglycidyl ether, stirring, coating the solution on an organic glass plate, drying the solvent at 70 ℃, heating to 85 ℃, baking for 2 hours, cooling and testing the surface resistance to be 3 multiplied by 106Ohm. Placing the sample piece in a room without packaging, contacting with air and light, and lowering the surface resistance to 9 × 109Ohm, 3 years.
Example 18
To 100 g of a 1.2% strength aqueous dispersion of a polymer represented by the formula (II) (wherein the mass ratio of the positively charged polymer to the 4-vinylbenzenesulfonic acid homopolymer was 1:2.5), 450 g of ethanol and 450 g of dimethyl sulfoxide were added to dilute the dispersion. 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 mixed thoroughlyMixing uniformly. To the above solution, 500 g (concentration 15%, solvent is ethanol to dimethyl sulfoxide mass ratio 1:1) of ethyl acrylate, methyl methacrylate, and copolymer solution of acrylic acid and methacrylic acid in a mass ratio of 10:84:3:3 was added, and stirred uniformly. Adding 0.15 g of biglycidyl hexahydrophthalate, stirring, coating the solution on an organic glass plate, drying the solvent at 70 ℃, heating to 85 ℃, baking for 2 hours, cooling and testing the surface resistance to be 3 multiplied by 106Ohm. Placing the sample piece in a room without packaging, contacting with air and light, and lowering the surface resistance to 9 × 109Ohm, 3 years.
Example 19
To 100 g of a 1.2% strength aqueous dispersion of a polymer represented by the formula (II) (wherein the mass ratio of the positively charged polymer to the 4-vinylbenzenesulfonic acid homopolymer was 1:2.5), 450 g of ethanol and 450 g of dimethyl sulfoxide were added to dilute the dispersion. 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-benzotriazol-2-yl) -6- (dodecyl) -4-methylphenol and 0.02 g of 2- (2' -hydroxy-3 ',5' -bis (. alpha.,. alpha. -dimethylbenzyl) phenyl) benzotriazole were added and mixed well. To the above solution, 500 g (concentration 15%, solvent is ethanol to dimethyl sulfoxide mass ratio 1:1) of ethyl acrylate, methyl methacrylate, and copolymer solution of acrylic acid and methacrylic acid in a mass ratio of 10:84:3:3 was added, and stirred uniformly. Adding 0.15 g of biglycidyl hexahydrophthalate, stirring, coating the solution on an organic glass plate, drying the solvent at 70 ℃, heating to 85 ℃, baking for 2 hours, cooling and testing the surface resistance to be 3 multiplied by 106Ohm. Placing the sample piece in a room without packaging, contacting with air and light, and lowering the surface resistance to 9 × 109Ohm, 3 years.
Comparative example 1
To a 1.2% concentration of a 1:2.5 aqueous dispersion of a polymer of the formula (II) wherein the mass ratio of the positively charged polymer to the 4-vinylbenzenesulfonic acid homopolymer is 1:2.5To 00 g was added 450 g propanol and 450 g dimethyl sulfoxide for dilution. To the above solution, 500 g (concentration 15%, solvent is propanol to dimethyl sulfoxide mass ratio 1:1) of methyl acrylate, methyl methacrylate, and copolymer solution of acrylic acid to methacrylic acid in a mass ratio of 10:84:3:3 was added, and stirred uniformly. Coating the solution on organic glass plate, drying the solvent at 70 deg.C, cooling, and testing the surface resistance to 1 × 106Ohm. Placing the sample piece in a room without packaging, contacting with air and light, and lowering the surface resistance to 9 × 109Ohm, 1 year time.
In this specification, the invention has been described with reference to specific embodiments thereof. It will, however, be evident that various modifications and changes may be made thereto without departing from the broader spirit and scope of the invention. The description is thus to be regarded as illustrative instead of limiting.

Claims (10)

1. An ionomer coating for removing surface charges, comprising the following components:
a host 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, and the functionality of the hydrogen bond group is more than or equal to 1;
a polar solvent.
2. The ionomer coating for dissipating surface charges of claim 1, wherein the acidic ionomer is a pure acidic ionomer or an acidic ionomer partially neutralized with basic groups.
3. The ionomer coating for dissipating surface charges according to claim 1 or 2, wherein the acidic ionomer is selected from one or more of homopolymers or copolymers formed from the following monomers:
acrylic acid, maleic acid, 4-vinylbenzenesulfonic acid, vinylsulfonic acid.
4. The ionomer coating for dissipating surface charges of claim 2, wherein the basic groups are provided by one or more of the following basic compounds:
alkali metal, amino, quaternary ammonium base, pyridine derivative, triazine, 2,4, 6-triphenyl-1, 3, 5-triazine, imidazole, benzimidazole, benzotriazole, oxazole, and a polymer having a repeating unit of the following formula (I) having a positive charge
Figure FDA0002863880330000011
5. The ionomer coating for removing surface charges of claim 2 or 4, wherein the number of moles of the basic groups < the number of moles of the acidic groups in the acidic ionomer.
6. The ionomer coating material of claim 2, 3 or 4, wherein the acidic ionomer is poly-4-vinylbenzenesulfonic acid and the basic groups are provided by a polymer having a positive charge and repeating units of formula (I), wherein the number of moles of positively charged groups in the polymer having a repeating unit of formula (I) is less than the number of moles of acidic groups in the acidic ionomer
Figure FDA0002863880330000012
Figure FDA0002863880330000021
7. The ionomer coating for dissipating surface charges of claim 1, wherein the primary crosslinker having both hydrogen bonding groups and base groups is selected from one or more of the following compounds:
amines containing a carbon hydroxyl group, pyridines containing a carbon hydroxyl group, imidazoles containing a carbon hydroxyl group, benzimidazoles containing a carbon hydroxyl group, benzotriazoles containing a carbon hydroxyl group, melamines containing a carbon hydroxyl group, 2,4, 6-triphenyl-1, 3-5-triazine containing a carbon hydroxyl group;
or the cross-linking agent with 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 hydroxy-substituted 2,4, 6-triphenyl-1, 3-5-triazine derivatives, diethanolamine, triethanolamine, tris (hydroxymethyl) aminomethane, bis (2-hydroxymethyl) amino-tris (hydroxymethyl) methane, N-dihydroxyethyldodecylamine, N-dihydroxyethyloctadecylamine, 2-hydroxymethylpyridine, 2-hydroxyethylpyridine, 2-pyridylpropanol, 2-pyridylbutanol, 3-hydroxypyridine, 3-hydroxymethylpyridine, 2- (3-pyridyl) ethanol, 1- (3-pyridyl) ethanol, 3-pyridylpropanol, 3-pyridylbutanol, 4-hydroxypyridine, 4-triphenylamine, 2, 4-triphenylamine, 3-triazine derivatives, diethanolamine, triethanolamine, tris (hydroxymethyl) methane, N-dihydroxyethyldodecylamine, N-dihydroxyethyloctadecylamine, 4-hydroxymethylpyridine, 4-hydroxyethylpyridine, 4-pyridylpropanol, 4-pyridinebutanol, 1- (2-hydroxyethyl) imidazole, 1-hydroxymethylbenzimidazole, 4-hydroxybenzimidazole, 2-methyl-5-hydroxybenzimidazole, melamine, benzoguanamine, 2- (2 '-hydroxy-3' -tert-butyl-5 '-methylphenyl) -5-chlorobenzotriazole, 2- (2' -hydroxy-3 ',5' -di-tert-butylphenyl) -benzotriazole, 2- (2 '-hydroxy-3', 5 '-dipentylphenyl) benzotriazole, 2- (2' -hydroxy-5 '-tert-octylphenyl) benzotriazole, 2- (2' -hydroxy-3 ',5' -bis (. alpha.,. alpha. -dimethylbenzyl) phenyl) benzotriazole, 2- (2H-benzotriazol-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-bis (2, 4-dimethylphenyl) -1,3, 5-triazine, 2- [2, 4-bis (2, 4-xylyl) -2- (1,3, 5-triazinyl) ] 5-octyloxyphenol, octyltriazone, 2- (4, 6-diphenyl-1, 3, 5-triazine-2) -5-n-hexylalkoxyphenol, bis-ethylethoxyphenol methoxyphenyl triazine, 2- [4- [ 2-hydroxy-3-tridecyloxypropyl ] 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 mixture;
the molar ratio of the monofunctional basic group in the crosslinking agent with the hydrogen bond group and the basic group to the acidic group in the acidic ionomer is 0.05-1.
8. The ionomer coating material for removing surface charges according to claim 1, further comprising an epoxy resin auxiliary cross-linking agent, wherein the functionality of the epoxy resin is not less than 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, diglycidyl hexahydrophthalate, epoxidized soybean oil, dimer acid diglycidyl ester, trimethylolpropane triglycidyl ether, glycerol triglycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, 4, 5-epoxycyclohexane-1, 2-dicarboxylic acid diglycidyl ester, 3' - (oxybis-methylene) bis (3-ethyl) oxetane, 3, 4-epoxycyclohexylmethyl 3, 4-epoxycyclohexyl formate, bis ((3, 4-epoxycyclohexyl) methyl) adipate, 1, 4-cyclohexanedimethanol (3, 4-epoxycyclohexanecarboxylic acid) ester;
the molar ratio of the epoxy group in the epoxy resin to the acidic group in the acidic ionomer is 0-0.1.
9. A method of preparing the ionomer coating for removing surface charges of any one of claims 1 to 8, comprising:
uniformly mixing the main resin and the acidic ionomer, and then adding a main cross-linking agent with hydrogen bond groups and basic groups to dissolve in a polar solvent to obtain the ionomer coating for eliminating surface charges;
or the preparation method comprises the step of adding epoxy resin to dissolve in a polar solvent.
10. A coating layer for removing surface charges, wherein the ionomer coating material for removing surface charges of any one of claims 1 to 8 is coated on a base material including a plastic substrate by means of doctor blade coating, curtain coating, gravure printing or screen printing, and the coating layer for removing surface charges is formed by drying a solvent at 85 ℃ or lower.
CN202011578812.6A 2020-12-28 2020-12-28 Ionomer coating for eliminating surface charge, preparation method thereof and corresponding coating Pending CN112724757A (en)

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CN115785813A (en) * 2022-11-25 2023-03-14 东莞理工学院 Super-hydrophilic porous coating with convertible transparency, preparation method and application thereof

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CN103173108A (en) * 2011-12-22 2013-06-26 深圳市百泉河实业有限公司 Environment-friendly washing-resistant antistatic coating and preparation method thereof
CN103666209A (en) * 2012-09-25 2014-03-26 深圳市百泉河实业有限公司 Environment-friendly static conductive paint suitable for polyethylene or polypropylene materials and preparation method thereof
CN110845943A (en) * 2019-10-30 2020-02-28 江西铜业技术研究院有限公司 Water-based transparent antistatic coating and preparation method thereof

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CN101040002A (en) * 2004-08-30 2007-09-19 信越聚合物株式会社 Conductive composition and conductive crosslinked material, capacitor and method for manufacturing same, antistatic coating composition, antistatic coat, antistatic film, optical filter and optical in
CN103173108A (en) * 2011-12-22 2013-06-26 深圳市百泉河实业有限公司 Environment-friendly washing-resistant antistatic coating and preparation method thereof
CN103666209A (en) * 2012-09-25 2014-03-26 深圳市百泉河实业有限公司 Environment-friendly static conductive paint suitable for polyethylene or polypropylene materials and preparation method thereof
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Publication number Priority date Publication date Assignee Title
CN115785813A (en) * 2022-11-25 2023-03-14 东莞理工学院 Super-hydrophilic porous coating with convertible transparency, preparation method and application thereof
CN115785813B (en) * 2022-11-25 2023-08-15 东莞理工学院 Super-hydrophilic porous coating with changeable transparency, preparation method and application thereof

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