Antifogging coating reaction monomer, resin composition and antifogging coating

Abstract

The invention relates to the technical field of coatings, and particularly discloses an anti-fog coating reaction monomer, a resin composition and an anti-fog coating. The anti-fog coating reactive monomer comprises the following materials in parts by weight: 89-95 parts of a polycondensation oligomer, 1.5-15 parts of an anionic reactant and 10-25 parts of an isocyanate acrylate monomer. The antifogging coating resin composition comprises the following materials in parts by weight: 100 parts of monomers, 150 parts of a polymerization solvent and 0.5-1 part of an initiator, the monomers comprise a reaction monomer, a vinyl monomer and a crosslinking monomer, and the reaction monomer is the antifogging coating reaction monomer. The anti-fog coating can be used for the surfaces of optical products such as lampshades and glasses, and has the advantages of lasting anti-fog and water resistance.

Description

Technical Field

[0001] The present application relates to the technical field of coatings, and more specifically, to an anti-fog coating reaction monomer, a resin composition and an anti-fog coating. Background Art

[0002] Transparent materials such as polymethyl methacrylate (PMMA), polycarbonate (PC), and polyethylene terephthalate (PET) are widely used in various vehicle lampshades because of their advantages of light weight, good impact resistance, low price, and easy molding and processing. However, when the headlights are turned on, synthetic resin materials will experience a sharp temperature change inside and outside the lamp housing under high humidity conditions. The moisture in the air inside the lampshade condenses and adheres to the surface of the lampshade, which easily produces small water droplets and fog. As a result, the lighting brightness decreases and may even endanger safety. In order to prevent the generation of such water droplets and fog, various methods have been proposed. For example, (1) directly coating a surfactant on the surface of the substrate; (2) coating an anti-fog coating containing a hydrophilic resin and a surfactant on the surface of the substrate; (3) forming a photocatalytic functional film on the surface of the substrate; (4) arranging a heating wire inside the substrate and heating the substrate to a temperature above the dew point after power is turned on.

[0003] However, although the (1) method has excellent initial anti-fog performance, the applied surfactant will be washed off quickly, resulting in the loss of the anti-fog effect. (2) The method achieves the anti-fog effect through the synergistic effect of hydrophilic resin and surfactant, and the anti-fog effect is relatively long-lasting, but the surfactant is a free small molecule after all, and will eventually be washed off, resulting in the loss of the anti-fog effect. In addition, the water resistance of the hydrophilic resin is low, which will cause coating defects. This is the mainstream method for anti-fogging of headlight covers at present. (3) Since the method forms a film of inorganic substances such as titanium oxide, the anti-fog performance requires ultraviolet light and has a destructive effect on the synthetic resin substrate. It is only suitable for inorganic materials such as glass. (4) The method has a good anti-fog effect, but there is a problem with power supply, and its use is greatly limited. This solution is used for the rearview mirror and rear windshield of the vehicle. Summary of the invention

[0004] In order to improve the durability and water resistance of the anti-fog coating, the present application provides an anti-fog coating reaction monomer, a resin composition and an anti-fog coating, which adopt the following technical scheme:

[0005] In a first aspect, the present application provides an anti-fog coating reaction monomer, comprising the following materials in parts by weight:

[0006] 89-95 parts of polycondensation oligomer;

[0007] 1.5-15 parts of anionic reactant;

[0008] 10-25 parts of isocyanate acrylate monomer;

[0009] The average molecular weight of the polycondensation oligomer is 500-2000, and the acid value of the polycondensation oligomer is (30-110) mgKOH / g;

[0010] The anion reactant is selected from any one of bicarbonate, carbonate or monobasic base;

[0011] The isocyanate acrylic monomer is selected from any one of 2-isocyanoethyl acrylate, 2-isocyanoethyl methacrylate, and 2-(2-isocyanatoethoxy)ethyl methacrylate.

[0012] Optionally, the polycondensation oligomer is obtained by polycondensation of a hydroxy acid containing a hydroxy group and a carboxyl group, and the carboxyl acid is an ε or higher hydroxy acid.

[0013] By adopting the above technical scheme, ε and above hydroxy acids are selected as the main components of the polycondensate. When heated, α-hydroxy acids are prone to dehydration between two molecules to form a ring, forming a cyclic compound. When heated, β-hydroxy acids are prone to intramolecular dehydration to form an unsaturated acid. When heated, γ-hydroxy acids and δ-hydroxy acids are prone to intramolecular dehydration to form a ring, forming a five-membered or six-membered cyclic lactone. ε and above hydroxy acids are conducive to polycondensation to form a reaction monomer with a suitable molecular weight, forming a long-chain polymer, which is conducive to the subsequent preparation of acrylic resin.

[0014] Optionally, the carboxylic acid is selected from any one of 6-hydroxyhexanoic acid, 7-hydroxyheptanoic acid, 8-hydroxyoctanoic acid, 9-hydroxynonanoic acid, 10-hydroxydecanoic acid, 12-hydroxylauric acid, and 12-hydroxystearic acid.

[0015] Optionally, the anion reactant is selected from any one of sodium bicarbonate, potassium bicarbonate, lithium bicarbonate, sodium carbonate, potassium carbonate, lithium carbonate, sodium hydroxide, potassium hydroxide, and lithium hydroxide.

[0016] In a second aspect, the present application provides an anti-fog coating resin composition, comprising the following materials in parts by weight:

[0017] 100 parts of monomer;

[0018] 150 parts of polymerization solvent;

[0019] Initiator 0.5-1 part;

[0020] The monomers include reactive monomers, vinyl monomers and cross-linking monomers;

[0021] The reactive monomer is the anti-fog coating reactive monomer described above;

[0022] The vinyl monomer is selected from any one or more of an aromatic vinyl monomer, a linear, branched or cyclic alkyl acrylate, and a vinyl monomer containing a nitrogen atom;

[0023] The crosslinking monomer is any one or more of a vinyl monomer containing a hydroxyl group and a vinyl monomer containing N-methylol or N-hydroxyalkoxymethylol.

[0024] By adopting the above technical scheme, under the initiation of the initiator, free radical polymerization is carried out between the reactive monomer, the vinyl monomer and the cross-linking monomer to form a comb-shaped polymer with a hydrophobic long carbon chain structure as the main chain and a hydrophilic functional group at the end of the longer branch chain. The hydrophilic functional group in the resin composition can make it difficult for water to spread on the surface of the coating film and form water beads, so as to achieve an anti-fog effect. The hydrophilic functional group is far away from the main chain at the end of the branch chain, so that the resin composition has an excellent anti-fog effect and a better water resistance effect.

[0025] Optionally, the vinyl monomer is selected from any one or more of methyl methacrylate, n-butyl methacrylate, n-butyl acrylate, isooctyl methacrylate, isooctyl acrylate, isobornyl methacrylate, N-vinyl pyrrolidone, and N,N-dimethylacrylamide.

[0026] Optionally, the cross-linking monomer is selected from any one or more of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, and hydroxymethyl acrylamide.

[0027] Optionally, the polymerization solvent is selected from any one or more of isopropanol, methanol, ethanol, ethyl acetate, acetone, butanone, propylene glycol methyl ether, ethylene glycol monobutyl ether, and water.

[0028] In a third aspect, the present application provides an anti-fog coating, which adopts the following technical solution:

[0029] An anti-fog coating comprises the following materials in parts by weight: 100 parts of a resin composition, 0-29.9 parts of a curing agent, 0.03 parts of a catalyst, 0.03 parts of a leveling agent, and 270-295 parts of a diluent. The resin composition is the anti-fog coating resin composition described above.

[0030] By adopting the above technical solution, a comb-shaped polymer with a hydrophobic long carbon chain structure as the main chain and a relatively hydrophilic functional group at the end of the longer side chain is used, so that the hydrophilic anion will not be too close to the main chain structure, so that the coating can obtain excellent anti-fog effect and water resistance. There is no need to add small molecular substances such as surfactants, and there will be no problem of a decrease in the long-term anti-fog effect due to the loss of surfactants.

[0031] Optionally, the curing agent is selected from blocked isocyanate, HDI biuret, HDI trimer, and amino resin.

[0032] Optionally, the blocked isocyanate is a diisocyanate blocked with phenol, ε-caprolactam, malonate, ketoxime or pyrazole.

[0033] Optionally, the amino resin is n-butanol etherified amino resin, isobutanol etherified amino resin, methanol etherified amino resin, or mixed etherified amino resin.

[0034] In summary, this application has the following beneficial effects:

[0035] 1. This application uses ε and above hydroxy acids as the main components of the polycondensate. When heated, α-hydroxy acids are prone to dehydration between two molecules to form a ring, forming a cyclic compound. When heated, β-hydroxy acids are prone to intramolecular dehydration to form unsaturated acids. When heated, γ-hydroxy acids and δ-hydroxy acids are prone to intramolecular dehydration to form a ring, forming a five-membered or six-membered cyclic lactone. ε and above hydroxy acids are conducive to polycondensation to form a reaction monomer with a suitable molecular weight, forming a long-chain polymer, which is conducive to the subsequent preparation of acrylic resin.

[0036] 2. In this application, under the initiation of the initiator, free radical polymerization can be carried out between the reactive monomers, vinyl monomers and cross-linking monomers to form a comb-like polymer with a hydrophobic long carbon chain structure as the main chain and a relatively long hydrophilic functional group as the side chain. The hydrophilic segments in the resin composition can make it difficult for water to spread on the surface of the coating film and form water beads, thereby improving the anti-fog effect of the resin composition. The hydrophilic functional group is far away from the main chain under the action of the side chain, so that the resin composition obtains excellent anti-fog effect and better water resistance.

[0037] 3. The comb-like polymer used in this application has anions at the end of its side chains that can provide sufficient hydrophilicity, and the effect of long-lasting anti-fog property can be achieved without the addition of small molecules such as surfactants, and there will be no problem of a decrease in the long-term anti-fog property due to the loss of surfactants. DETAILED DESCRIPTION

[0038] The present application is further described in detail below with reference to the embodiments.

[0039] Example

[0040] Example 1

[0041] In one aspect, the present application provides an anti-fog coating reaction monomer, comprising a polycondensation oligomer, an anion reactant, and an isocyanate acrylate monomer.

[0042] Wherein, the average molecular weight of the polycondensation oligomer is 500-2000, and the acid value of the polycondensation oligomer is (30-110) mgKOH / g;

[0043] Specifically, in this embodiment, the carboxylic acid is 6-hydroxycaproic acid, the anion reactant is sodium bicarbonate, and the isocyanate acrylic monomer is ethyl 2-isocyanoacrylate.

[0044] The preparation of the reaction monomer is as follows: 100g of 6-hydroxycaproic acid and 5g of toluene are mixed, refluxed at (160-220)°C for dehydration and esterification, and the acid value is detected to be 110mgKOH / g, and the temperature is reduced to obtain a polycondensation oligomer. 14.75g of sodium bicarbonate is added to the reactor and mixed, and the reaction is ≤1mgKOH / g. The water and toluene are evaporated by reduced pressure distillation, and then 24.77g of ethyl 2-isocyanoacrylate is added, and the reaction is carried out at 30-60°C for 1-5h to prepare the reaction monomer M001.

[0045] In a second aspect, the present application provides an anti-fog coating resin composition, including a monomer, a polymerization solvent, an initiator and an anionic reactant, and the specific masses are shown in the table below.

[0046] Among them, the monomers include reactive monomers, vinyl monomers and cross-linking monomers. The reactive monomers are the reactive monomers prepared as described above. In this embodiment, the vinyl monomers are methyl methacrylate, n-butyl methacrylate and N-vinyl pyrrolidone, the cross-linking monomer is hydroxyethyl acrylate, the polymerization solvents are isopropanol, acetone and ethylene glycol monobutyl ether, and the initiator is azobisisobutyronitrile.

[0047] The preparation of the resin composition is as follows:

[0048] First, 38 g of reaction monomer M001, 25 g of methyl methacrylate, 5 g of n-butyl methacrylate, 15 g of N-vinyl pyrrolidone monomer and 1 g of azobisisobutyronitrile were mixed and set aside.

[0049] 90 g of isopropanol, 30 g of acetone and 30 g of ethylene glycol monobutyl ether were added into a reactor, heated and stirred to (60-90)°C, a mixture of monomer and initiator was added dropwise for (3-5) h, the mixture was kept warm for (3-5) h, and the material was cooled and discharged to obtain a resin composition B001.

[0050] In a third aspect, the present application provides an anti-fog coating, comprising a resin composition B001, a blocked isocyanate, a catalyst and a diluent.

[0051] Specifically, 100 g of the resin composition and 29.99 g of blocked isocyanate were taken. BL3475, 0.05 g of dibutyltin dilaurate, 0.03 g of a commercially available polyether-modified silicone leveling agent, 5.0 g of isopropyl alcohol, 30 g of ethyl acetate, 90 g of propylene glycol methyl ether, and 100 g of ethylene glycol monobutyl ether were mixed to prepare an anti-fog coating.

[0052] Example 2

[0053] The difference from Example 1 is:

[0054] In one aspect, the present application provides an anti-fog coating reaction monomer, comprising a polycondensation oligomer, an anion reactant, and an isocyanate acrylate monomer.

[0055] Wherein, the average molecular weight of the polycondensation oligomer is 500-2000, and the acid value of the polycondensation oligomer is (30-110) mgKOH / g;

[0056] Specifically, in this embodiment, the carboxylic acid is 7-hydroxyheptanoic acid, the anion reactant is sodium carbonate, and the isocyanate acrylic monomer is ethyl 2-isocyanoacrylate.

[0057] The preparation of the reaction monomer is as follows: 100g of 7-hydroxyheptanoic acid and 5g of toluene are mixed, and refluxed at (160-220)°C for dehydration and esterification, and the acid value is detected to be 95mgKOH / g, and the temperature is lowered and cooled to obtain a polycondensation oligomer;

[0058] The reaction monomer is prepared as follows: 90.43g of polycondensation oligomer and 8.12g of sodium bicarbonate are mixed and reacted to ≤1mgKOH / g. Water and aromatic hydrocarbons are distilled off by reduced pressure distillation, 23.76g of 2-isocyanoethyl methacrylate is added, and the reaction is carried out at 30-60°C for 1-5h to prepare the reaction monomer M002.

[0059] In a second aspect, the present application provides an anti-fog coating resin composition, including a monomer, a polymerization solvent, an initiator and an anionic reactant, and the specific masses are shown in Table 2 below.

[0060] The preparation of the resin composition is as follows:

[0061] 38.5 g of reaction monomer M002, 20 g of methyl methacrylate, 5 g of n-butyl acrylate, 6 g of isooctyl acrylate, 15 g of N,N-dimethylacrylamide and 0.8 g of azobisisobutyronitrile were mixed for later use.

[0062] 40 g of isopropanol, 75 g of methanol and 35 g of acetone were added into a reactor, heated and stirred to (60-90) °C, a mixture of monomer and initiator was added dropwise for (3-5) h, kept warm for (3-5) h, cooled and discharged to obtain resin composition B002.

[0063] In a third aspect, the present application provides an anti-fog coating, comprising a resin composition B002, a blocked isocyanate, a catalyst and a diluent.

[0064] Specifically, 100 g of the resin composition and 22.48 g of blocked isocyanate were taken. BL3370, 0.05 g of dibutyltin dilaurate, 0.03 g of a commercially available polyether-modified silicone leveling agent, 47.5 g of isopropyl alcohol, 80 g of propylene glycol methyl ether, and 150 g of ethylene glycol monobutyl ether were mixed to prepare an anti-fog coating.

[0065] Example 3

[0066] The difference from Example 1 is:

[0067] In one aspect, the present application provides an anti-fog coating reaction monomer, comprising a polycondensation oligomer, an anion reactant, and an isocyanate acrylate monomer.

[0068] Wherein, the average molecular weight of the polycondensation oligomer is 500-2000, and the acid value of the polycondensation oligomer is (30-110) mgKOH / g;

[0069] Specifically, in this embodiment, the carboxylic acid is 8-hydroxyoctanoic acid, the anion reactant is sodium hydroxide, and the isocyanate acrylic monomer is 2-(2-isocyanatoethoxy)ethyl methacrylate.

[0070] The preparation of the reaction monomer is as follows: 100g of 8-hydroxyoctanoic acid and 5g of toluene are mixed, and refluxed at (160-220)°C for dehydration and esterification, and the acid value is detected to be 80mgKOH / g, and the temperature is lowered and cooled to obtain a polycondensation oligomer;

[0071] The reaction monomer is prepared as follows: 91.09g of polycondensation oligomer and 5.20g of sodium hydroxide are mixed and reacted to ≤1mgKOH / g. Water and aromatic hydrocarbons are distilled off by reduced pressure distillation, 25.88g of 2-(2-isocyanatoethoxy)ethyl methacrylate is added, and the reaction is carried out at 30-60°C for 1-5h to prepare the reaction monomer M003.

[0072] In a second aspect, the present application provides an anti-fog coating resin composition, including a monomer, a polymerization solvent, an initiator and an anionic reactant, and the specific masses are shown in Table 2 below.

[0073] The preparation of the resin composition is as follows:

[0074] 40 g of reaction monomer M003, 20 g of methyl methacrylate, 10 g of n-butyl methacrylate, 5 g of isooctyl methacrylate, 8.5 g of isobornyl methacrylate, 5 g of N-vinyl pyrrolidone, 11.5 g of hydroxypropyl acrylate and 0.8 g of azobisisobutyronitrile were mixed for later use.

[0075] 45 g of ethyl acetate, 75 g of butanone and 30 g of ethylene glycol monobutyl ether were added into a reactor, heated and stirred to (60-90) °C, a mixture of monomer and initiator was added dropwise for (3-5) h, the mixture was kept warm for (3-5) h, and the mixture was cooled and discharged to obtain a resin composition B003.

[0076] In a third aspect, the present application provides an anti-fog coating, comprising a resin composition B003, an isocyanate, a catalyst and a diluent.

[0077] Specifically, 100 g of resin composition B003 and 9.01 g of isocyanate N75, 0.05 g of dibutyltin dilaurate, 0.03 g of a commercially available polyether-modified silicone leveling agent, 150 g of ethyl acetate, and 141 g of ethylene glycol monobutyl ether were mixed to prepare an anti-fog coating.

[0078] Example 4

[0079] In one aspect, the present application provides an anti-fog coating reaction monomer, comprising a polycondensation oligomer, an anion reactant, and an isocyanate acrylate monomer.

[0080] Wherein, the average molecular weight of the polycondensation oligomer is 500-2000, and the acid value of the polycondensation oligomer is (30-110) mgKOH / g;

[0081] Specifically, in this embodiment, the carboxylic acid is 9-hydroxynonanoic acid, the anion reactant is potassium bicarbonate, and the isocyanate acrylic monomer is ethyl 2-isocyanoacrylate.

[0082] The preparation of the reaction monomer is as follows: 100g of 9-hydroxynonanoic acid and 5g of toluene are mixed, and refluxed at (160-220)°C for dehydration and esterification, and the acid value is detected to be 65mgKOH / g, and the temperature is lowered and cooled to obtain a polycondensation oligomer;

[0083] The reaction monomer is prepared as follows: 91.57g of polycondensation oligomer and 10.62g of potassium bicarbonate are mixed and reacted to ≤1mgKOH / g. Water and aromatic hydrocarbons are distilled off by reduced pressure distillation, 14.97g of 2-isocyanoethyl methacrylate is added, and the reaction is carried out at 30-60°C for 1-5h to prepare the reaction monomer M004.

[0084] In a second aspect, the present application provides an anti-fog coating resin composition, including a monomer, a polymerization solvent, an initiator and an anionic reactant, and the specific masses are shown in Table 2 below.

[0085] The preparation of the resin composition is as follows:

[0086] 42 g of reaction monomer M004, 30 g of methyl methacrylate, 10 g of isobornyl methacrylate, 9.5 g of N,N-dimethylacrylamide, 8.5 g of hydroxypropyl methacrylate and 0.8 g of azobisisobutyronitrile were mixed for later use.

[0087] 45 g of isopropanol, 50 g of methanol, 25 g of acetone and 30 g of ethylene glycol monobutyl ether were added into a reactor, heated and stirred to (60-90) °C, a mixture of monomer and initiator was added dropwise for (3-5) h, the mixture was kept warm for (3-5) h, and the material was cooled and discharged to obtain a resin composition B004.

[0088] In a third aspect, the present application provides an anti-fog coating, comprising a resin composition B004, a blocked isocyanate, a catalyst and a diluent.

[0089] Specifically, 100 g of resin composition B004 and 10.75 g of blocked isocyanate were taken. BI 7992, 0.05 g of dibutyltin dilaurate, 0.03 g of a commercially available polyether-modified silicone leveling agent, 50 g of isopropyl alcohol, 140 g of propylene glycol monobutyl ether, and 100 g of ethylene glycol monobutyl ether were mixed to prepare an anti-fog coating.

[0090] Example 5

[0091] In one aspect, the present application provides an anti-fog coating reaction monomer, comprising a polycondensation oligomer, an anion reactant, and an isocyanate acrylate monomer.

[0092] Wherein, the average molecular weight of the polycondensation oligomer is 500-2000, and the acid value of the polycondensation oligomer is (30-110) mgKOH / g;

[0093] Specifically, in this embodiment, the carboxylic acid is 10-hydroxydecanoic acid, the anion reactant is potassium carbonate, and the isocyanate acrylic monomer is ethyl 2-isocyanoacrylate.

[0094] The preparation of the reaction monomer is as follows: 100g of 10-hydroxydecanoic acid and 5g of xylene are mixed, and refluxed at (160-220)°C for dehydration and esterification, and the acid value is detected to be 50mgKOH / g, and the temperature is lowered and cooled to obtain a polycondensation oligomer;

[0095] The reaction monomer is prepared as follows: 91.90g of polycondensation oligomer and 4.1g of potassium carbonate are mixed and reacted to ≤1mgKOH / g. Water and aromatic hydrocarbons are distilled off by reduced pressure distillation, 11.56g of 2-isocyanoethyl methacrylate is added, and the reaction is carried out at 30-60°C for 1-5h to prepare the reaction monomer M005.

[0096] In a second aspect, the present application provides an anti-fog coating resin composition, including a monomer, a polymerization solvent, an initiator and an anionic reactant, and the specific masses are shown in Table 2 below.

[0097] The preparation of the resin composition is as follows:

[0098] 44.5 g of reaction monomer M005, 25 g of methyl methacrylate, 10 g of isobornyl methacrylate, 5.5 g of n-butyl acrylate, 1.5 g of N,N-dimethylacrylamide, 15 g of hydroxymethylacrylamide and 0.7 g of azobisisobutyronitrile were mixed for later use.

[0099] 40 g of isopropanol, 50 g of methanol, 20 g of ethyl acetate, 40 g of butanone and 50 g of ethylene glycol monobutyl ether were put into a reactor, heated with stirring to (60-90) °C, a mixture of monomer and initiator was added dropwise for (3-5) h, the mixture was kept warm for (3-5) h, and the material was cooled and discharged to obtain a resin composition B005.

[0100] In a third aspect, the present application provides an anti-fog coating, comprising a resin composition B004, a blocked isocyanate, a catalyst and a diluent.

[0101] Specifically, 100 g of resin composition B005 and 10.75 g of blocked isocyanate BI 7992, 5 g of dodecylbenzene sulfonic acid, 0.03 g of a commercially available polyether-modified silicone leveling agent, 45 g of isopropyl alcohol, 50 g of ethyl acetate, and 150 g of ethylene glycol monobutyl ether were mixed to prepare an anti-fog coating.

[0102] Example 6

[0103] In one aspect, the present application provides an anti-fog coating reaction monomer, comprising a polycondensation oligomer, an anion reactant, and an isocyanate acrylate monomer.

[0104] Wherein, the average molecular weight of the polycondensation oligomer is 500-2000, and the acid value of the polycondensation oligomer is (30-110) mgKOH / g;

[0105] Specifically, in this embodiment, the carboxylic acid is 12-hydroxylauric acid, the anion reactant is potassium hydroxide, and the isocyanate acrylic monomer is 2-isocyanoethyl methacrylate.

[0106] The preparation of the reaction monomer is as follows: 100g of 12-hydroxylauric acid and 5g of xylene are mixed, and refluxed at (160-220)°C for dehydration and esterification, and the acid value is detected to be 40mgKOH / g, and the temperature is lowered and cooled to obtain a polycondensation oligomer;

[0107] The reaction monomer is prepared as follows: 92.86g of polycondensation oligomer and 9.15g of potassium hydroxide are mixed and reacted to ≤1mgKOH / g. Water and aromatic hydrocarbons are distilled off by reduced pressure distillation, 10.27g of 2-isocyanoethyl methacrylate is added, and the reaction is carried out at 30-60°C for 1-5h to prepare the reaction monomer M006.

[0108] In a second aspect, the present application provides an anti-fog coating resin composition, including a monomer, a polymerization solvent, an initiator and an anionic reactant, and the specific masses are shown in Table 2 below.

[0109] The preparation of the resin composition is as follows:

[0110] 55 g of reaction monomer M006, 20 g of methyl methacrylate, 10 g of isobornyl methacrylate, 1.5 g of N,N-dimethylacrylamide, 13.5 g of hydroxyethyl acrylate and 0.5 g of azobisisobutyronitrile were mixed for later use.

[0111] Heat 50g of ethanol, 70g of butanone and 30g of propylene glycol methyl ether to (60-90)°C with stirring, add dropwise a mixture of monomer and initiator for (3-5)h, keep warm for (3-5)h, cool and discharge to obtain resin composition B006.

[0112] In a third aspect, the present application provides an anti-fog coating, comprising a resin composition B004, an amino resin, a catalyst and a diluent.

[0113] Specifically, 100 g of the resin composition B006, 15 g of the amino resin CYMEL 325, 5 g of dodecylbenzene sulfonic acid, 0.03 g of a commercially available polyether-modified silicone leveling agent, 120 g of isopropyl alcohol, and 100 g of propylene glycol methyl ether were mixed to prepare an anti-fog coating.

[0114] Example 7

[0115] In one aspect, the present application provides an anti-fog coating reaction monomer, comprising a polycondensation oligomer, an anion reactant, and an isocyanate acrylate monomer.

[0116] Wherein, the average molecular weight of the polycondensation oligomer is 500-2000, and the acid value of the polycondensation oligomer is (30-110) mgKOH / g;

[0117] Specifically, in this embodiment, the carboxyl acid is 12-hydroxystearic acid, the anion reactant is lithium carbonate, and the isocyanate acrylic monomer is 2-(2-isocyanatoethoxy)ethyl methacrylate.

[0118] The preparation of the reaction monomer is as follows: 100g 12-hydroxystearic acid and 5g xylene are mixed, and refluxed at (160-220)°C for dehydration and esterification, and the acid value is detected to be 40mgKOH / g, and the temperature is lowered and cooled to obtain a polycondensation oligomer;

[0119] The reaction monomer is prepared as follows: 94.92g of polycondensation oligomer and 1.88g of lithium carbonate are mixed and reacted to ≤1mgKOH / g. Water and aromatic hydrocarbons are distilled off by reduced pressure distillation, 10.11g of 2-(2-isocyanatoethoxy)ethyl methacrylate is added, and the reaction is carried out at 30-60°C for 1-5h to prepare the reaction monomer M007.

[0120] In a second aspect, the present application provides an anti-fog coating resin composition, including a monomer, a polymerization solvent, an initiator and an anionic reactant, and the specific masses are shown in Table 2 below.

[0121] The preparation of the resin composition is as follows:

[0122] 55 g of reaction monomer M007, 11 g of methyl methacrylate, 15 g of isobornyl methacrylate, 19 g of hydroxypropyl acrylate and 0.5 g of azobisisobutyronitrile were mixed for later use.

[0123] 30 g of ethyl acetate, 50 g of acetone, 40 g of butanone and 30 g of ethylene glycol monobutyl ether were added into a reactor, heated and stirred to (60-90) °C, a mixture of monomer and initiator was added dropwise for (3-5) h, the mixture was kept warm for (3-5) h, and the mixture was cooled and discharged to obtain a resin composition B007.

[0124] In a third aspect, the present application provides an anti-fog coating, comprising a resin composition B004, an isocyanate, a catalyst and a diluent.

[0125] Specifically, 100 g of resin composition B007 and 12.49 g of isocyanate N3390, 0.05 g of dibutyltin dilaurate, 0.03 g of a commercially available polyether-modified silicone leveling agent, 137.5 g of ethyl acetate, and 150 g of ethylene glycol monobutyl ether were mixed to prepare an anti-fog coating.

[0126] Table 1 Addition amount of each component of the reaction monomer in Examples 1-7

[0127]

[0128]

[0129] Table 2 Addition amount of each component of the resin composition of Examples 1-7

[0130]

[0131]

[0132] Table 3 Addition amount of each component of anti-fog coating of Examples 1-7

[0133]

[0134]

[0135] The anti-fog coatings prepared in Examples 1-7 were subjected to a board preparation test by air spraying on PC at (80-120)°C for (20-30) min, with a coating thickness of (1-5) μm.

[0136] The test method is as follows:

[0137] ① Adhesion: According to GB / T 9286-2021, 100 grid tests with 1mm spacing tape.

[0138] ② Anti-fogging property: Place the test piece with the coating surface facing downward at a height of 5 cm from the surface of 80°C warm water and observe with the naked eye for 10 seconds to see if there is any fogging.

[0139] ③ Water resistance: According to GB / T 30648.2-2015, immerse the test piece in 80℃ water for 4h, dry it naturally at room temperature for 1h, observe the appearance and conduct anti-fog test.

[0140] ④ Heat resistance: According to GB / T 1735-2009, the test piece was placed at 120°C for 240 hours, cooled at room temperature for 1 hour, and then the anti-fog test was performed.

[0141] ⑤ Anti-fog durability: repeat the anti-fog test 10 times continuously, dry naturally at room temperature for 1 hour each time, and the anti-fog performance can still meet the requirements after 10 times.

[0142] The specific results are as follows:

[0143] Table 4

[0144]

[0145]

[0146] This specific embodiment is merely an explanation of the present application and is not a limitation of the present application. After reading this specification, those skilled in the art may make modifications to the present embodiment without any creative contribution as needed, but such modifications are protected by the patent law as long as they are within the scope of the claims of the present application.

Claims

1. An anti-fog coating reaction monomer, characterized in that: The materials include the following parts by weight: 89-95 parts of polycondensation oligomer; 1.5-15 parts of anionic reactant; 10-25 parts of isocyanate acrylate monomer; The average molecular weight of the polycondensation oligomer is 500-2000, and the acid value of the polycondensation oligomer is (30-110) mgKOH / g; The anion reactant is selected from any one of bicarbonate, carbonate or monobasic base; The isocyanate acrylic monomer is selected from any one of 2-ethyl isocyanoacrylate, 2-ethyl isocyanomethacrylate, and 2-(2-isocyanatoethoxy)ethyl methacrylate.

2. The anti-fog coating reaction monomer according to claim 1, characterized in that: The polycondensation oligomer is obtained by polycondensation of a hydroxy acid containing a hydroxyl group and a carboxyl group, and the carboxyl acid is an ε-hydroxy acid or above.

3. The anti-fog coating reaction monomer according to claim 2, characterized in that: The carboxylic acid is selected from any one of 6-hydroxycaproic acid, 7-hydroxyheptanoic acid, 8-hydroxyoctanoic acid, 9-hydroxynonanoic acid, 10-hydroxydecanoic acid, 12-hydroxylauric acid and 12-hydroxystearic acid.

4. The anti-fog coating reaction monomer according to claim 1, characterized in that: The anion reactant is selected from any one of sodium bicarbonate, potassium bicarbonate, lithium bicarbonate, sodium carbonate, potassium carbonate, lithium carbonate, sodium hydroxide, potassium hydroxide, and lithium hydroxide.

5. An anti-fog coating resin composition, characterized in that: Including the following materials by weight: 100 parts of monomer; 150 parts of polymerization solvent; Initiator 0.5-1 part; The monomers include reactive monomers, vinyl monomers and cross-linking monomers; The reactive monomer is the anti-fog coating reactive monomer according to any one of claims 1 to 4; The vinyl monomer is selected from any one or more of an aromatic vinyl monomer, a linear, branched or cyclic alkyl acrylate, and a vinyl monomer containing a nitrogen atom; The crosslinking monomer is any one or more of a vinyl monomer containing a hydroxyl group, a vinyl monomer containing an N-hydroxymethyl group or an N-hydroxyalkoxymethylol group.

6. The anti-fog coating resin composition according to claim 5, characterized in that: The vinyl monomer is selected from any one or more of methyl methacrylate, n-butyl methacrylate, n-butyl acrylate, isooctyl methacrylate, isooctyl acrylate, isobornyl methacrylate, N-vinyl pyrrolidone, and N,N-dimethylacrylamide.

7. The anti-fog coating resin composition according to claim 5, characterized in that: The cross-linking monomer is selected from any one or more of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, and hydroxymethyl acrylamide.

8. The anti-fog coating resin composition according to claim 5, characterized in that: The polymerization solvent is selected from any one or more of isopropanol, methanol, ethanol, ethyl acetate, acetone, butanone, propylene glycol methyl ether, ethylene glycol monobutyl ether and water.

9. An anti-fog coating, characterized in that: Including the following materials by weight: 100 parts of resin composition; Curing agent 0-29.9 parts; 0.03 parts of catalyst; 0.03 parts of leveling agent; 270-295 parts of diluent; The resin composition is the anti-fog coating resin composition according to any one of claims 5 to 8.

10. The anti-fog coating resin composition according to claim 9, characterized in that: The curing agent is selected from blocked isocyanate, HDI biuret, HDI trimer, and amino resin; The blocked isocyanate is a diisocyanate blocked with phenol, ε-caprolactam, malonate, ketoxime or pyrazole; The amino resin is n-butanol etherified amino resin, isobutanol etherified amino resin, methanol etherified amino resin, and mixed etherified amino resin.

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