An anti-fog coating reactive monomer, resin composition, and anti-fog coating

Abstract

The application relates to the technical field of paint, and particularly discloses an anti-fogging paint reaction monomer, a resin composition and an anti-fogging paint. The anti-fogging paint reaction monomer comprises the following materials in parts by weight: a polycondensation oligomer 89-95 parts, an anion reactant 1.5-15 parts and an isocyanate acrylate monomer 10-25 parts. The anti-fogging paint resin composition comprises the following materials in parts by weight: a monomer 100 parts, a polymerization solvent 150 parts and an initiator 0.5-1 part. The monomer comprises a reaction monomer, a vinyl monomer and a cross-linking monomer, and the reaction monomer is the anti-fogging paint reaction monomer. The anti-fogging paint can be used on the surface of optical products such as lampshades and glasses, and has the advantages of persistent anti-fogging and water resistance.

Description

Technical Field

[0001] This application relates to the technical field of coatings, and more specifically, to an anti-fog coating reactive monomer, resin composition, and anti-fog coating. Background Technology

[0002] Transparent materials such as polymethyl methacrylate (PMMA), polycarbonate (PC), and polyethylene terephthalate (PET) have advantages such as light weight, good impact resistance, low price, and easy molding and processing, and are therefore widely used in various vehicle lamp covers. However, in high humidity environments, when the headlight is turned on, the synthetic resin material will experience a rapid temperature change inside and outside the lamp housing. The moisture in the air inside the lamp cover will condense and adhere to the surface of the lamp cover, easily producing small water droplets and fog. As a result, the lighting brightness will decrease, and it 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 the substrate surface with surfactants; (2) coating the substrate surface with an anti-fog coating containing hydrophilic resin and surfactants; (3) forming a photocatalytic functional film on the substrate surface; (4) arranging heating wires inside the substrate and heating the substrate temperature above the dew point after energizing, etc.

[0003] However, (1) although the initial anti-fogging performance of the method is excellent, the applied surfactant will be washed away quickly, resulting in the loss of the anti-fogging effect. (2) The method achieves the anti-fogging effect through the synergistic effect of hydrophilic resin and surfactant, and the anti-fogging effect is relatively long-lasting. However, the surfactant is a free small molecule and will eventually be washed away, resulting in the loss of the anti-fogging effect. Moreover, the hydrophilic resin has low water resistance, which will cause coating defects. This is currently the mainstream method for anti-fogging of car headlight covers. (3) Since the method forms a film of inorganic materials such as titanium dioxide, the anti-fogging performance requires ultraviolet light and has a destructive effect on synthetic resin substrates. It is only suitable for inorganic materials such as glass. (4) The method has a good anti-fogging effect, but there is a power supply problem, which greatly limits its application. This solution is used for vehicle rearview mirrors and rear windshields. Summary of the Invention

[0004] To improve the durability and water resistance of anti-fog coatings, this application provides an anti-fog coating reactive monomer, a resin composition, and an anti-fog coating, employing the following technical solution:

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

[0006] 89-95 parts of condensation oligomers;

[0007] 1.5-15 parts of anionic reactant;

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

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

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

[0011] The isocyanate acrylic monomer is selected from any one of ethyl 2-isocyanoacrylate, ethyl 2-isocyanomethacrylate, and 2-(2-isocyanoethoxy)ethyl methacrylate.

[0012] Optionally, the condensation oligomer is obtained by condensation polymerization of a hydroxy acid containing one hydroxyl group and one carboxyl group, wherein the carboxyl acid is an ε- or higher hydroxy acid.

[0013] By adopting the above technical solution, ε- and higher hydroxy acids are selected as the main components of the condensation polymer. α-hydroxy acids readily undergo intermolecular dehydration and ring formation upon heating, generating cyclic compounds. β-hydroxy acids readily undergo intramolecular dehydration upon heating, generating unsaturated acids. γ- and δ-hydroxy acids readily undergo intramolecular dehydration and ring formation upon heating, generating five- or six-membered cyclic lactones. ε- and higher hydroxy acids are beneficial for condensation polymerization to form reactive monomers with suitable molecular weights, forming long-chain polymers, which is advantageous for the subsequent preparation of acrylic resins.

[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 anionic 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] Secondly, this application provides an anti-fog coating resin composition comprising the following materials in parts by weight:

[0017] 100 units per unit;

[0018] 150 parts of polymerization solvent;

[0019] Initiator 0.5-1 part;

[0020] The monomers include reactive monomers, vinyl monomers, and crosslinking monomers;

[0021] The reactive monomer is the antifog coating reactive monomer described above;

[0022] The vinyl monomer is selected from any one or more of aromatic vinyl monomers, alkyl acrylates having straight chains, branched chains or cyclic structures, and vinyl monomers containing nitrogen atoms.

[0023] The crosslinking monomer is any one or more of a vinyl monomer containing hydroxyl groups and a vinyl monomer containing N-hydroxymethyl or N-hydroxyalkoxyhydroxymethyl.

[0024] By employing the above technical solution, under the initiation of an initiator, the reactive monomers, vinyl monomers, and crosslinking monomers undergo free radical polymerization to form a comb-like polymer with a hydrophobic main chain and hydrophilic functional groups at the ends of the relatively long branches. The hydrophilic functional groups in the resin composition prevent water from spreading on the coating surface and forming droplets, thus achieving an anti-fogging effect. The hydrophilic functional groups are located far from the main chain at the ends of the branches, enabling the resin composition to achieve both excellent anti-fogging and superior water resistance.

[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-vinylpyrrolidone, and N,N-dimethylacrylamide.

[0026] Optionally, the crosslinking monomer is selected from any one or more of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, and hydroxymethylacrylamide.

[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] Thirdly, this 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 resin composition, 0-29.9 parts of curing agent, 0.03 parts of catalyst, 0.03 parts of leveling agent, and 270-295 parts of diluent, wherein the resin composition is the anti-fog coating resin composition described above.

[0030] By adopting the above technical solution, a comb-like polymer with a hydrophobic long carbon chain main chain and relatively hydrophilic functional groups on the ends of the longer branches is used. This prevents hydrophilic anions from getting too close to the main chain structure, giving the coating excellent anti-fogging effect and water resistance. No external surfactants or other small molecule substances are needed, thus avoiding the problem of decreased long-term anti-fogging performance due to surfactant loss.

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

[0032] Optionally, the blocked isocyanate is a diisocyanate blocked with phenol, ε-caprolactam, malonic acid ester, ketooxime, or pyrazole.

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

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

[0035] 1. This application selects ε- and higher hydroxy acids as the main components of the condensation polymer. α-hydroxy acids readily undergo intermolecular dehydration and ring formation upon heating, generating cyclic compounds. β-hydroxy acids readily undergo intramolecular dehydration upon heating, generating unsaturated acids. γ- and δ-hydroxy acids readily undergo intramolecular dehydration and ring formation upon heating, generating five- or six-membered cyclic lactones. ε- and higher hydroxy acids are beneficial for condensation polymerization to form reactive monomers with suitable molecular weights, forming long-chain polymers, which is beneficial for the subsequent preparation of acrylic resins.

[0036] 2. In this application, under the initiation of the initiator, the reactive monomers, vinyl monomers, and crosslinking monomers can undergo free radical polymerization to form a comb-like polymer with a hydrophobic long carbon chain main chain and relatively long hydrophilic functional groups in the side chains. The hydrophilic segments in the resin composition prevent water from spreading on the coating surface and forming droplets, thus improving the anti-fogging effect of the resin composition. The hydrophilic functional groups are located further from the main chain due to the action of the side chains, enabling the resin composition to achieve both excellent anti-fogging and good water resistance.

[0037] 3. The comb-like polymer used in this application has anions at the ends of its branches that can provide sufficient hydrophilicity. It can achieve long-lasting anti-fogging properties without the need for the addition of surfactants or other small molecule substances, and will not cause a decrease in the long-term effectiveness of anti-fogging due to surfactant loss. Detailed Implementation

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

[0039] Example

[0040] Example 1

[0041] On the one hand, this application provides an anti-fog coating reactive monomer, comprising condensation oligomers, anionic reactants, and isocyanate acrylate monomers.

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

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

[0044] The monomer was prepared as follows: 100g of 6-hydroxyhexanoic acid and 5g of toluene were mixed and refluxed at (160-220)℃ for dehydration and esterification. The acid value was found to be 110mgKOH / g. After cooling, a condensation oligomer was obtained. 14.75g of sodium bicarbonate was added to the reactor and the mixture was reacted until the KOH / g concentration was ≤1mg. The water and toluene were removed by vacuum distillation. Then, 24.77g of ethyl 2-isocyanate was added, and the mixture was reacted at 30-60℃ for 1-5 hours to prepare the monomer M001.

[0045] Secondly, this application provides an anti-fog coating resin composition, comprising monomers, polymerization solvents, initiators, and anionic reactants, the specific quantities of which are shown in the table below.

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

[0047] The resin composition is prepared as follows:

[0048] First, mix 38g of reactive monomer M001, 25g of methyl methacrylate, 5g of n-butyl methacrylate, 15g of N-vinylpyrrolidone monomer and 1g of azobisisobutyronitrile and set aside.

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

[0050] Thirdly, this application provides an anti-fog coating comprising a resin composition B001, a blocked isocyanate, a catalyst, and a diluent.

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

[0052] Example 2

[0053] The difference from Example 1 is as follows:

[0054] On the one hand, this application provides an anti-fog coating reactive monomer, comprising condensation oligomers, anionic reactants, and isocyanate acrylate monomers.

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

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

[0057] The reaction monomers were prepared as follows: 100g of 7-hydroxyheptanoic acid and 5g of toluene were mixed and refluxed at (160-220)℃ for dehydration and esterification. The acid value was found to be 95mgKOH / g. The mixture was then cooled to obtain the condensation oligomer.

[0058] The reactive monomer was prepared as follows: 90.43 g of condensation oligomer and 8.12 g of sodium bicarbonate were mixed and reacted until ≤1 mg KOH / g. The water and aromatics were removed by vacuum distillation, and 23.76 g of ethyl 2-isocyanomethacrylate was added. The mixture was reacted at 30-60℃ for 1-5 h to prepare the reactive monomer M002.

[0059] Secondly, this application provides an anti-fog coating resin composition, comprising monomers, polymerization solvents, initiators and anionic reactants, the specific quantities of which are shown in Table 2 below.

[0060] The resin composition is prepared as follows:

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

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

[0063] Thirdly, this application provides an anti-fog coating comprising a resin composition B002, a blocked isocyanate, a catalyst, and a diluent.

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

[0065] Example 3

[0066] The difference from Example 1 is as follows:

[0067] On the one hand, this application provides an anti-fog coating reactive monomer, comprising condensation oligomers, anionic reactants, and isocyanate acrylate monomers.

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

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

[0070] The reaction monomers were prepared as follows: 100g of 8-hydroxyoctanoic acid and 5g of toluene were mixed and refluxed at (160-220)℃ for dehydration and esterification. The acid value was found to be 80mgKOH / g. The mixture was then cooled to obtain the condensation oligomer.

[0071] The reactive monomer was prepared as follows: 91.09 g of condensation oligomer and 5.20 g of sodium hydroxide were mixed and reacted until ≤1 mg KOH / g. The water and aromatics were removed by vacuum distillation, and 25.88 g of 2-(2-isocyanate ethoxy)ethyl methacrylate was added. The mixture was reacted at 30-60℃ for 1-5 h to prepare the reactive monomer M003.

[0072] Secondly, this application provides an anti-fog coating resin composition, comprising monomers, polymerization solvents, initiators and anionic reactants, the specific quantities of which are shown in Table 2 below.

[0073] The resin composition is prepared as follows:

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

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

[0076] Thirdly, this application provides an anti-fog coating comprising a resin composition B003, an isocyanate, a catalyst, and a diluent.

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

[0078] Example 4

[0079] On the one hand, this application provides an anti-fog coating reactive monomer, comprising condensation oligomers, anionic reactants, and isocyanate acrylate monomers.

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

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

[0082] The reaction monomers were prepared as follows: 100g of 9-hydroxynonanoic acid and 5g of toluene were mixed and refluxed at (160-220)℃ for dehydration and esterification. The acid value was found to be 65mgKOH / g. The mixture was then cooled to obtain the condensation oligomer.

[0083] The reactive monomer was prepared as follows: 91.57 g of condensation oligomer and 10.62 g of potassium bicarbonate were mixed and reacted until ≤1 mg KOH / g. The water and aromatics were removed by vacuum distillation, and 14.97 g of ethyl 2-isocyanomethacrylate was added. The mixture was reacted at 30-60℃ for 1-5 h to prepare the reactive monomer M004.

[0084] Secondly, this application provides an anti-fog coating resin composition, comprising monomers, polymerization solvents, initiators and anionic reactants, the specific quantities of which are shown in Table 2 below.

[0085] The resin composition is prepared as follows:

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

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

[0088] Thirdly, this application provides an anti-fog coating comprising a resin composition B004, a blocked isocyanate, a catalyst, and a diluent.

[0089] Specifically, take 100g of resin composition B004 and 10.75g of blocked isocyanate. An anti-fog coating was prepared by mixing BI 7992, 0.05g dibutyltin dilaurate, 0.03g commercially available polyether-modified silicone leveling agent, 50g isopropanol, 140g propylene glycol monobutyl ether, and 100g ethylene glycol monobutyl ether.

[0090] Example 5

[0091] On the one hand, this application provides an anti-fog coating reactive monomer, comprising condensation oligomers, anionic reactants, and isocyanate acrylate monomers.

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

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

[0094] The reaction monomers were prepared as follows: 100g of 10-hydroxydecanoic acid and 5g of xylene were mixed and refluxed at (160-220)℃ for dehydration and esterification. The acid value was found to be 50mgKOH / g. The mixture was then cooled to obtain the condensation oligomer.

[0095] The reactive monomer was prepared as follows: 91.90 g of condensation oligomer and 4.1 g of potassium carbonate were mixed and reacted until ≤1 mg KOH / g. The water and aromatics were removed by vacuum distillation, and 11.56 g of ethyl 2-isocyanomethacrylate was added. The mixture was reacted at 30-60℃ for 1-5 h to prepare the reactive monomer M005.

[0096] Secondly, this application provides an anti-fog coating resin composition, comprising monomers, polymerization solvents, initiators and anionic reactants, the specific quantities of which are shown in Table 2 below.

[0097] The resin composition is prepared as follows:

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

[0099] 40g isopropanol, 50g methanol, 20g ethyl acetate, 40g butanone, and 50g ethylene glycol monobutyl ether were added to a reactor and heated and stirred to (60-90)℃. A mixture of monomer and initiator was added dropwise for (3-5)h, kept at the temperature for (3-5)h, cooled, and discharged to obtain resin composition B005.

[0100] Thirdly, this application provides an anti-fog coating comprising a resin composition B004, a blocked isocyanate, a catalyst, and a diluent.

[0101] Specifically, take 100g of resin composition B005 and 10.75g of blocked isocyanate. An anti-fog coating was prepared by mixing BI 7992, 5g dodecylbenzenesulfonic acid, 0.03g commercially available polyether-modified silicone leveling agent, 45g isopropanol, 50g ethyl acetate, and 150g ethylene glycol monobutyl ether.

[0102] Example 6

[0103] On the one hand, this application provides an anti-fog coating reactive monomer, comprising condensation oligomers, anionic reactants, and isocyanate acrylate monomers.

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

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

[0106] The reaction monomers were prepared as follows: 100g of 12-hydroxylauric acid and 5g of xylene were mixed and refluxed at (160-220)℃ for dehydration and esterification. The acid value was found to be 40mgKOH / g. The mixture was then cooled to obtain the condensation oligomer.

[0107] The reactive monomer was prepared as follows: 92.86 g of condensation oligomer and 9.15 g of potassium hydroxide were mixed and reacted until ≤1 mg KOH / g. The water and aromatics were removed by vacuum distillation, and 10.27 g of ethyl 2-isocyanomethacrylate was added. The mixture was reacted at 30-60℃ for 1-5 h to prepare the reactive monomer M006.

[0108] Secondly, this application provides an anti-fog coating resin composition, comprising monomers, polymerization solvents, initiators and anionic reactants, the specific quantities of which are shown in Table 2 below.

[0109] The resin composition is prepared as follows:

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

[0111] 50g ethanol, 70g butanone, and 30g propylene glycol methyl ether were heated and stirred to (60-90)℃. A mixture of monomer and initiator was added dropwise for (3-5)h, kept at this temperature for (3-5)h, cooled, and discharged to obtain resin composition B006.

[0112] Thirdly, this application provides an anti-fog coating comprising a resin composition B004, an amino resin, a catalyst, and a diluent.

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

[0114] Example 7

[0115] On the one hand, this application provides an anti-fog coating reactive monomer, comprising condensation oligomers, anionic reactants, and isocyanate acrylate monomers.

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

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

[0118] The reaction monomers were prepared as follows: 100g of 12-hydroxystearic acid and 5g of xylene were mixed and refluxed at (160-220)℃ for dehydration and esterification. The acid value was found to be 40mgKOH / g. The mixture was then cooled to obtain the condensation oligomer.

[0119] The reactive monomer was prepared as follows: 94.92 g of condensation oligomer and 1.88 g of lithium carbonate were mixed and reacted until ≤1 mg KOH / g. The water and aromatics were removed by vacuum distillation, and 10.11 g of 2-(2-isocyanate ethoxy)ethyl methacrylate was added. The mixture was reacted at 30-60℃ for 1-5 h to prepare the reactive monomer M007.

[0120] Secondly, this application provides an anti-fog coating resin composition, comprising monomers, polymerization solvents, initiators and anionic reactants, the specific quantities of which are shown in Table 2 below.

[0121] The resin composition is prepared as follows:

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

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

[0124] Thirdly, this application provides an anti-fog coating comprising a resin composition B004, an isocyanate, a catalyst, and a diluent.

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

[0126] Table 1. Amounts of each component added to the reactants in Examples 1-7

[0127]

[0128]

[0129] Table 2. Amounts of each component added to the resin compositions in Examples 1-7

[0130]

[0131]

[0132] Table 3. Addition amounts of each component in the antifog coatings of Examples 1-7

[0133]

[0134]

[0135] The anti-fog coatings prepared in Examples 1-7 were tested on a board by air spraying on PC, and baked at (80-120)℃ for (20-30) min, with a coating thickness of (1-5) μm.

[0136] The testing method is as follows:

[0137] ① Adhesion, according to GB / T 9286-2021, 1mm spacing tape cross-cut adhesion test.

[0138] ② Anti-fogging performance: Hold the test piece 5cm above the surface of 80℃ warm water with the coated side facing down and observe for 10 seconds to see if fogging occurs.

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

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

[0141] ⑤ Anti-fog durability: Repeat the anti-fog test 10 times consecutively, and allow it to air dry at room temperature for 1 hour each time. The anti-fog performance still meets the requirements after 10 tests.

[0142] The specific results are shown in the table below:

[0143] Table 4

[0144]

[0145]

[0146] This specific embodiment is merely an explanation of this application and is not intended to limit it. After reading this specification, those skilled in the art can make modifications to this embodiment without contributing any inventive step, but such modifications are protected by patent law as long as they fall within the scope of the claims of this application.

Claims

1. A reactive monomer for anti-fog coatings, characterized in that, The materials include the following parts by weight: 89-95 parts of condensation oligomers; 1.5-15 parts of anionic reactant; 10-25 parts of isocyanate acrylate monomer; The average molecular weight of the condensation oligomer is 500-2000, and the acid value of the condensation oligomer is (30-110) mgKOH / g; The anionic reactant is selected from any one of bicarbonate, carbonate, or monobasic base. The isocyanate acrylic monomer is selected from any one of 2-isocyanate ethyl acrylate, 2-isocyanate ethyl methacrylate, and 2-(2-isocyanate ethoxy) ethyl methacrylate. The condensation oligomer is obtained by condensation polymerization of a hydroxy acid containing one hydroxyl group and one carboxyl group, wherein the hydroxy acid is an ε- or higher hydroxy acid.

2. The anti-fog coating reactive monomer according to claim 1, characterized in that: The hydroxy 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.

3. The anti-fog coating reactive monomer according to claim 1, characterized in that: The anionic 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.

4. An anti-fog coating resin composition, characterized in that, Includes the following parts by weight of materials: 100 units per unit; 150 parts of polymerization solvent; Initiator 0.5-1 part; The monomers include reactive monomers, vinyl monomers, and crosslinking monomers; The reactive monomer is the antifog coating reactive monomer according to any one of claims 1-3; The vinyl monomer is selected from any one or more of aromatic vinyl monomers, alkyl acrylates having straight chains, branched chains or cyclic structures, and vinyl monomers containing nitrogen atoms. The crosslinking monomer is any one or more of the following: a vinyl monomer containing a hydroxyl group, a vinyl monomer containing N-hydroxymethyl or N-hydroxyalkoxyhydroxymethyl.

5. The anti-fog coating resin composition according to claim 4, 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-vinylpyrrolidone, and N,N-dimethylacrylamide.

6. The anti-fog coating resin composition according to claim 4, characterized in that: The crosslinking monomer is selected from any one or more of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, and hydroxymethylacrylamide.

7. The anti-fog coating resin composition according to claim 4, 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.

8. An anti-fog coating, characterized in that, Includes the following parts by weight of materials: 100 parts of resin composition; Hardener 0-29.9 parts; 0.03 parts catalyst; 0.03 parts leveling agent; 270-295 parts of diluent; The resin composition is the antifog coating resin composition according to any one of claims 5-7.

9. The anti-fog coating resin composition according to claim 8, 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 by phenol, ε-caprolactam, malonate, ketooxime or pyrazole; The amino resin is n-butanol etherified amino resin, isobutanol etherified amino resin, methanol etherified amino resin, or mixed etherified amino resin.

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