Photocuring antifogging coating

Abstract

The invention relates to the technical field of coatings, and particularly discloses a photocuring anti-fog coating. The photocuring anti-fog coating comprises the following raw materials in parts by weight: 8 parts of a monomer; 30 parts of light-cured resin; 60 parts of a solvent; 0.8 part of a photoinitiator; 0.03 part of an auxiliary agent; the light-cured resin is a comb polymer with a hydrophobic long carbon chain main chain, a hydrophilic functional group branch chain and double bonds. The anti-fog coating can be used for the surfaces of optical products such as car windows and glasses, and has the advantages of lasting anti-fog effect, rapid light curing and the like.

Description

Technical Field

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

[0002] There are a large number of products related to optics in our daily life, such as automobile glass, window glass of buildings, bathroom mirrors, instrument panels, glasses, protective glasses, etc. However, in places with high humidity or large temperature differences, these optical surfaces that are either transparent or reflective will easily form fog that affects vision. The general defogging method is to use air conditioning to heat the window surface, increase the condensation point of water, and keep the window surface in a dry state, so as to prevent fogging and ensure visibility when the vehicle is driving.

[0003] Anti-fog functional coatings include hydrophilic anti-fog coatings. Surfactants are used more frequently in hydrophilic anti-fog coatings. The principle is: the surfactant is directly coated or blended into other film-forming matrices, and the "dissolution" of the surfactant molecules is used to make it easier for water droplets to spread on the surface to form a water film rather than water droplets, which will not affect the optical properties of the surface. However, the effect of this anti-fog coating is not long-lasting. In photocuring coatings, because surfactants have good compatibility with water, they are incompatible with low-polarity or non-polar substances, and are basically in a phase separation state with the added monomers, and cannot play a hydrophilic effect in photocuring coatings. Summary of the invention

[0004] In order to improve the anti-fog effect of the light-curing anti-fog coating, the present application provides a light-curing anti-fog coating, which adopts the following technical solution:

[0005] The present application provides a light-curing anti-fog coating, comprising the following raw materials in parts by weight:

[0006] 8 parts of monomer;

[0007] 30 parts of light-curing resin;

[0008] 60 parts of solvent;

[0009] 0.8 parts of photoinitiator;

[0010] 0.03 parts of additives;

[0011] The photocurable resin is a polymer having a hydrophobic long carbon chain main chain, a hydrophilic functional group side chain and a double bond.

[0012] By adopting the above technical scheme, a photocurable resin with a hydrophobic long carbon chain structure and a relatively long hydrophilic functional group in the side chain is used as the main material of the anti-fog coating. The hydrophilic segment can make the water on the surface of the coating spread and not easy to form water beads. The hydrophilic functional group is far away from the main chain under the action of the side chain, so that the hydrophilic anion will not be too close to the main chain structure, so that the coating obtains excellent anti-fog effect and water-resistant effect. And due to the introduction of double bonds, it can be decomposed under the initiation of the photoinitiator to form free radicals and polymerize with the monomer to form a film quickly. In summary, it is preferred to use a comb-like polymer with a hydrophobic long carbon chain main chain, a hydrophilic functional group side chain and a double bond as a photocurable resin, which can polymerize single-molecule monomers with monomers and form a film quickly to obtain a highly water-resistant and anti-fog photocurable coating.

[0013] Optionally, the photocurable resin is prepared as follows: react the comb polymer with isophorone diisocyanate at 50±5° C., detect the NCO content to determine the degree of reaction, continue to add hydroxyl-containing acrylate monomers, increase the temperature, continue the reaction, and detect the NCO content to determine the reaction endpoint.

[0014] By adopting the above technical scheme, the preparation method of the photocurable resin is optimized. Since the two isocyanates in isophorone diisocyanate have different activities, they react preferentially at low temperature, so that the hydroxyl group in the comb polymer reacts with the more active isocyanate group in isophorone diisocyanate. Then, the temperature is raised, and the other isocyanate group with poor activity in isophorone diisocyanate reacts with the hydroxyl group in the acrylate monomer containing a hydroxyl group, thereby successfully introducing a double bond structure into the comb polymer, so that the photocurable resin can polymerize with the monomer under light initiation and form a film, so that the coating obtains excellent photocuring effect, anti-fog, water resistance and other excellent properties.

[0015] Optionally, the comb polymer comprises the following raw materials in parts by weight:

[0016] 38-55 parts of macromonomer;

[0017] 45-62 parts of reactive monomer;

[0018] 100 parts of solvent;

[0019] Initiator 0.5-1 part;

[0020] The reactive monomers include linear, branched or cyclic alkyl acrylates and hydroxyl-containing acrylate monomers.

[0021] By adopting the above technical solution, under the initiation of the initiator, free radical polymerization can be carried out between the macromolecular monomer and the reactive monomer to form a hydrophobic polymer with a long carbon chain structure of a hydrophobic main chain and a relatively long hydrophilic functional group in the side chain. The hydrophilic chain segments in the comb-like polymer 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 comb-like polymer. The hydrophilic functional group is far away from the main chain under the action of the side chain, so that the comb-like polymer has an excellent anti-fog effect and a better water resistance effect.

[0022] Optionally, the linear, branched or cyclic alkyl acrylate is selected from any one or more of methyl methacrylate, n-butyl (meth)acrylate, isooctyl (meth)acrylate and isobornyl methacrylate.

[0023] Optionally, the solvent is selected from any one or more of ethyl acetate, acetone, and butanone.

[0024] Optionally, the hydroxyl-containing acrylate monomer is selected from any one or more of hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, and hydroxybutyl (meth)acrylate.

[0025] Optionally, the initiator is selected from any one of azobisisobutyronitrile and dibenzoyl peroxide.

[0026] Optionally, the macromonomer comprises the following raw materials in parts by weight:

[0027] 89-95 parts of polycondensation oligomer;

[0028] 1.5-15 parts of anionic reactant;

[0029] 15-30 parts of isocyanate acrylate monomer;

[0030] The average molecular weight of the polycondensation oligomer is 500-1200, and the acid value of the polycondensation oligomer is 50-110;

[0031] The anion reactant is selected from any one of bicarbonate, carbonate or monobasic base;

[0032] The isocyanate acrylate monomer is selected from any one of 2-isocyanoethyl acrylate, 2-isocyanoethyl methacrylate, and 2-(2-isocyanatoethoxy)ethyl methacrylate.

[0033] Optionally, auxiliary agents are added during the preparation of the photocurable resin, and the auxiliary agents include catalysts and inhibitors.

[0034] By adopting the above technical solution, preferably a catalyst is added during the preparation of the photocurable resin to promote the reaction between the comb polymer and isophorone diisocyanate, and the introduction of the inhibitor can ensure that the double bond group can be stably connected during the reaction.

[0035] Optionally, the catalyst may be dibutyltin dilaurate.

[0036] Optionally, the polymerization inhibitor may be p-hydroxyanisole.

[0037] Optionally, the monomer is selected from any one or more of trimethylolpropane triacrylate (TMPTA), pentaerythritol triacrylate (PETA), ethoxylated trimethylolpropane triacrylate (EO9TMPTA), and dipentaerythritol hexaacrylate (DPHA).

[0038] Optionally, the photoinitiator is selected from 1-hydroxy-cyclohexylphenyl ketone (184) or 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (TPO).

[0039] In summary, this application has the following beneficial effects:

[0040] 1. Since the present application adopts a photocurable resin with a hydrophobic long carbon chain structure as the main chain and a relatively long hydrophilic functional group in the side chain as the main material of the anti-fog coating, the hydrophilic segment can make the water on the surface of the coating spread and not easily form water beads. The hydrophilic functional group is far away from the main chain under the action of the side chain, so that the hydrophilic anion will not be too close to the main chain structure, so that the coating obtains excellent anti-fog effect and water-resistant effect. And due to the introduction of double bonds, it can decompose under the initiation of photoinitiator, form free radicals and polymerize with monomers to form a film quickly. In summary, it is preferred to use a comb-like polymer with a hydrophobic long carbon chain main chain, a hydrophilic functional group side chain and a double bond as a photocurable resin, which can make single-molecule monomers polymerize with monomers and form a film quickly to obtain a highly water-resistant and anti-fog photocurable coating.

[0041] 2. In the present application, it is preferred to introduce double bond groups into the photocurable resin, utilize the polymerization between the double bond groups in the resin and the monomers, promote the reaction between the photocurable resin and the monomer polymer, and reduce the possibility of excessive free photocurable resin leading to poor coating performance.

[0042] 3. In the process of preparing the photocurable resin, a catalyst is added to promote the polymerization between the macromonomer and isophorone diisocyanate, and the introduction of the polymerization inhibitor can ensure that the double bond group can be stably connected during the reaction. DETAILED DESCRIPTION

[0043] The present application is further described in detail below with reference to the embodiments.

[0044] Example

[0045] Example 1

[0046] The present application provides a photocurable anti-fog coating, comprising 8 g of monomer, 30 g of photocurable resin, 60 g of solvent, 0.8 g of photoinitiator and 0.03 g of auxiliary agent;

[0047] Among them, in this embodiment, the monomers are trimethylolpropane triacrylate and pentaerythritol triacrylate of equal mass; the photoinitiator is 1-hydroxy-cyclohexyl phenyl ketone and 2,4,6-trimethylbenzoyl-diphenylphosphine oxide in a mass ratio of 3:1; the auxiliary agent is a leveling agent, and the leveling agent is a commercially available polyether-modified silicone leveling agent; the solvent includes isopropyl alcohol, butanone and propylene glycol methyl ether in a mass ratio of 6:1:5.

[0048] Photocurable resin has a comb-like polymer with a hydrophobic long carbon chain main chain, hydrophilic functional group side chains and double bonds. The hydrophilic functional groups on the side chains in the photocurable resin are far away from the main chain, that is, the hydrophilic anions in the side chains will not be too close to the main chain structure, so that the coating can obtain excellent anti-fog effect and water resistance effect.

[0049] The preparation of the photocurable resin is as follows: take 100g of comb polymer B001 and 16.27g of isophorone diisocyanate to react at 50±5°C, detect the NCO content to determine the degree of reaction, continue to add 8.5g of hydroxyethyl acrylate, add 50ppm of p-hydroxyanisole and 100ppm of dibutyltin dilaurate, raise the temperature to 70°C, continue the reaction, and detect the NCO content to determine the reaction endpoint.

[0050] The preparation of the comb-like polymer is as follows: 38 g of the macromonomer M001, 30 g of methyl methacrylate, 5 g of n-butyl methacrylate, 10 g of n-butyl acrylate, 17 g of hydroxyethyl acrylate and 1 g of azobisisobutyronitrile are mixed for later use, 70 g of ethyl acetate and 30 g of acetone are put into a reactor, heated with stirring to (60-90) ° C, a mixture of the monomer and the initiator is added dropwise for (3-5) h, the mixture is kept warm for (3-5) h, and the material is cooled and discharged to obtain a comb-like polymer B001.

[0051] The preparation of the macromonomer is as follows: 100g of 6-hydroxycaproic acid and 5g of toluene are mixed, and refluxed at (160-220)°C for dehydration and esterification. The acid value is detected to be 110mgKOH / g, and the temperature is lowered to obtain a polycondensation oligomer; 14.75g of sodium bicarbonate is added to the mixture and reacted to ≤1mgKOH / g. The water and aromatic hydrocarbons are distilled off under reduced pressure, and 24.77g of ethyl 2-isocyanoacrylate is added, and the reaction is carried out at 30-60°C for 1-5h to prepare the macromonomer M001.

[0052] The photocurable anti-fog coating is prepared as follows: monomers, photocurable resin, solvent, photoinitiator and auxiliary agent are taken respectively by weight, stirred and mixed to obtain the anti-fog coating.

[0053] Example 2

[0054] The present application provides a photocurable anti-fog coating, comprising 8 g of monomer, 30 g of photocurable resin, 60 g of solvent, 0.8 g of photoinitiator and 0.03 g of auxiliary agent;

[0055] Among them, in this embodiment, the monomer is pentaerythritol triacrylate; the photoinitiator is 1-hydroxy-cyclohexyl phenyl ketone and 2,4,6-trimethylbenzoyl-diphenylphosphine oxide in a mass ratio of 3:1; the auxiliary agent is a leveling agent, and the leveling agent is a commercially available polyether-modified silicone leveling agent; the solvent includes isopropanol, n-butanol, butanone and propylene glycol methyl ether in a mass ratio of 6:3:1:2.

[0056] Photocurable resin has a comb-like polymer with a hydrophobic long carbon chain main chain, hydrophilic functional group side chains and double bonds. The hydrophilic functional groups on the side chains in the photocurable resin are far away from the main chain, that is, the hydrophilic anions in the side chains will not be too close to the main chain structure, so that the coating can obtain excellent anti-fog effect and water resistance effect.

[0057] The preparation of the photocurable resin is as follows: take 100g of comb polymer B002 and 13.24g of isophorone diisocyanate to react at 50±5°C, detect the NCO content to determine the degree of reaction, continue to add 7.75g of hydroxyethyl methacrylate, add 50ppm of p-hydroxyanisole and 100ppm of dibutyltin dilaurate, raise the temperature to 70°C, continue the reaction, and detect the NCO content to determine the reaction endpoint.

[0058] The preparation of the comb-like polymer is as follows: 38.5 g of the macromonomer M002, 30 g of methyl methacrylate, 10 g of n-butyl methacrylate, 6 g of isooctyl acrylate, 15.5 g of hydroxyethyl acrylate and 1 g of azobisisobutyronitrile are mixed for later use, 50 g of ethyl acetate, 20 g of acetone and 30 g of butanone are put into a reactor, heated with stirring to (60-90) ° C, a mixture of the monomers and the initiator is added dropwise for (3-5) h, the mixture is kept warm for (3-5) h, and the material is cooled and discharged to obtain a comb-like polymer B002.

[0059] The preparation of the macromonomer is as follows: 100g 7-hydroxyheptanoic acid and 5g toluene are mixed, refluxed at (160-220)°C for dehydration and esterification, and the acid value is detected to be 100mgKOH / g, and the temperature is lowered to obtain a polycondensation oligomer; 8.56g sodium carbonate is added to the mixture, and the mixture is reacted to ≤1mgKOH / g. The water and aromatic hydrocarbons are distilled off under reduced pressure, and 25.05g 2-isocyanoethyl methacrylate is added, and the mixture is reacted at 30-60°C for 1-5h to obtain the macromonomer M002.

[0060] The photocurable anti-fog coating is prepared as follows: monomers, photocurable resin, solvent, photoinitiator and auxiliary agent are taken respectively by weight, stirred and mixed to obtain the anti-fog coating.

[0061] Example 3

[0062] The present application provides a photocurable anti-fog coating, comprising 8 g of monomer, 30 g of photocurable resin, 60 g of solvent, 0.8 g of photoinitiator and 0.03 g of auxiliary agent;

[0063] Among them, the monomers in this embodiment include pentaerythritol triacrylate and dipentaerythritol hexaacrylate in a mass ratio of 4:1; the photoinitiator is 1-hydroxy-cyclohexyl phenyl ketone and 2,4,6-trimethylbenzoyl-diphenylphosphine oxide in a mass ratio of 3:1; the auxiliary agent is a leveling agent, and the leveling agent is a commercially available polyether-modified silicone leveling agent; the solvent includes isopropyl alcohol, butanone and propylene glycol methyl ether in a mass ratio of 6:1:5.

[0064] Photocurable resin has a comb-like polymer with a hydrophobic long carbon chain main chain, hydrophilic functional group side chains and double bonds. The hydrophilic functional groups on the side chains in the photocurable resin are far away from the main chain, that is, the hydrophilic anions in the side chains will not be too close to the main chain structure, so that the coating can obtain excellent anti-fog effect and water resistance effect.

[0065] The preparation of the photocurable resin is as follows: take 100g of comb polymer B003 and 12.81g of isophorone diisocyanate to react at 50±5°C, detect the NCO content to determine the degree of reaction, continue to add 8.31g of hydroxybutyl acrylate, add 50ppm of p-hydroxyanisole and 100ppm of dibutyltin dilaurate, raise the temperature to 70°C, continue the reaction, and detect the NCO content to determine the reaction endpoint.

[0066] The preparation of the comb-like polymer is as follows: 40g of the macromonomer M003, 20g of methyl methacrylate, 10g of n-butyl methacrylate, 5g of isooctyl methacrylate, 10g of isobornyl methacrylate, 15g of hydroxypropyl acrylate and 1.0g of azobisisobutyronitrile are mixed for later use, 50g of ethyl acetate, 20g of acetone and 30g of butanone are put into a reactor, heated and stirred to (60-90)°C, a mixture of the monomers and the initiator is added dropwise for (3-5)h, the mixture is kept warm for (3-5)h, and the material is cooled and discharged to obtain a comb-like polymer B003.

[0067] The preparation of the macromonomer is as follows: 100g of 8-hydroxyoctanoic acid and 5g of toluene are mixed, and refluxed at (160-220)°C for dehydration and esterification. The acid value is detected to be 90mgKOH / g, and the temperature is lowered to obtain a polycondensation oligomer; 5.86g of sodium hydroxide is added to the mixture and reacted to ≤1mgKOH / g. The water and aromatic hydrocarbons are distilled off under reduced pressure, and 29.21g of 2-(2-isocyanatoethoxy)ethyl methacrylate is added, and the reaction is carried out at 30-60°C for 1-5h to prepare the macromonomer M003.

[0068] The photocurable anti-fog coating is prepared as follows: monomers, photocurable resin, solvent, photoinitiator and auxiliary agent are taken respectively by weight, stirred and mixed to obtain the anti-fog coating.

[0069] Example 4

[0070] The present application provides a photocurable anti-fog coating, comprising 8 g of monomer, 30 g of photocurable resin, 60 g of solvent, 0.8 g of photoinitiator and 0.03 g of auxiliary agent;

[0071] In this embodiment, the monomers include trimethylolpropane triacrylate, (9) ethoxylated trimethylolpropane triacrylate and dipentaerythritol hexaacrylate in a mass ratio of 1:2:1; the photoinitiator is 1-hydroxy-cyclohexyl phenyl ketone and 2,4,6-trimethylbenzoyl-diphenylphosphine oxide in a mass ratio of 3:1; the auxiliary agent is a leveling agent, and the leveling agent is a commercially available polyether-modified silicone leveling agent; the solvent includes isopropyl alcohol, n-butanol, butanone and propylene glycol methyl ether in a mass ratio of 6:3:1:2.

[0072] Photocurable resin has a comb-like polymer with a hydrophobic long carbon chain main chain, hydrophilic functional group side chains and double bonds. The hydrophilic functional groups on the side chains in the photocurable resin are far away from the main chain, that is, the hydrophilic anions in the side chains will not be too close to the main chain structure, so that the coating can obtain excellent anti-fog effect and water resistance effect.

[0073] The preparation of the photocurable resin is as follows: take 100g of comb polymer B004 and 11.57g of isophorone diisocyanate to react at 50±5°C, detect the NCO content to determine the degree of reaction, continue to add 7.50g of hydroxypropyl methacrylate, add 50ppm of p-hydroxyanisole and 100ppm of dibutyltin dilaurate, raise the temperature to 70°C, continue the reaction, and detect the NCO content to determine the reaction endpoint.

[0074] The preparation of the comb-like polymer is as follows: 42g of the macromonomer M004, 33g of methyl methacrylate, 10g of isobornyl methacrylate, 15g of hydroxybutyl acrylate and 1.0g of dibenzoyl peroxide are mixed for later use, 70g of ethyl acetate and 30g of butanone are put into a reactor, heated and stirred to (60-90)°C, a mixture of the monomer and the initiator is added dropwise for (3-5)h, the mixture is kept warm for (3-5)h, and the material is cooled and discharged to obtain a comb-like polymer B004.

[0075] The preparation of the macromonomer is as follows: 100g of 9-hydroxynonanoic acid and 5g of toluene are mixed, and refluxed at (160-220)°C for dehydration and esterification. The acid value is detected to be 80mgKOH / g, and the temperature is lowered to obtain a polycondensation oligomer; 13.14g of potassium bicarbonate is added to the mixture, and the mixture is reacted to ≤1mgKOH / g. The water and aromatic hydrocarbons are distilled off under reduced pressure, and 18.52g of ethyl 2-isocyanoacrylate is added, and the mixture is reacted at 30-60°C for 1-5h to obtain the macromonomer M004.

[0076] The photocurable anti-fog coating is prepared as follows: monomers, photocurable resin, solvent, photoinitiator and auxiliary agent are taken respectively by weight, stirred and mixed to obtain the anti-fog coating.

[0077] Example 5

[0078] The present application provides a photocurable anti-fog coating, comprising 8 g of monomer, 30 g of photocurable resin, 60 g of solvent, 0.8 g of photoinitiator and 0.03 g of auxiliary agent;

[0079] In this embodiment, the monomers include trimethylolpropane triacrylate, pentaerythritol triacrylate and (9) ethoxylated trimethylolpropane triacrylate in a mass ratio of 2:1:1; the photoinitiator is 1-hydroxy-cyclohexyl phenyl ketone and 2,4,6-trimethylbenzoyl-diphenylphosphine oxide in a mass ratio of 3:1; the auxiliary agent is a leveling agent, and the leveling agent is a commercially available polyether-modified silicone leveling agent; the solvent includes isopropyl alcohol, butanone and propylene glycol methyl ether in a mass ratio of 6:1:5.

[0080] Photocurable resin has a comb-like polymer with a hydrophobic long carbon chain main chain, hydrophilic functional group side chains and double bonds. The hydrophilic functional groups on the side chains in the photocurable resin are far away from the main chain, that is, the hydrophilic anions in the side chains will not be too close to the main chain structure, so that the coating can obtain excellent anti-fog effect and water resistance effect.

[0081] The preparation of the photocurable resin is as follows: take 100g of comb polymer B005 and 11.56g of isophorone diisocyanate to react at 50±5°C, detect the NCO content to determine the degree of reaction, continue to add 6.77g of hydroxypropyl acrylate, add 50ppm of p-hydroxyanisole and 100ppm of dibutyltin dilaurate, raise the temperature to 70°C, continue the reaction, and detect the NCO content to determine the reaction endpoint.

[0082] The preparation of the comb-like polymer is as follows: 44.5 g of the macromonomer M005, 25 g of methyl methacrylate, 10 g of isobornyl methacrylate, 5.5 g of n-butyl acrylate, 15 g of hydroxypropyl acrylate and 1.0 g of dibenzoyl peroxide are mixed for later use, 70 g of ethyl acetate and 30 g of butanone are added into a reactor, heated and stirred to (60-90) ° C, a mixture of the monomers and the initiator is added dropwise for (3-5) h, the mixture is kept warm for (3-5) h, and the material is cooled and discharged to obtain a comb-like polymer B005.

[0083] The preparation of the macromonomer is as follows: 100g 10-hydroxydecanoic acid and 5g xylene are mixed, refluxed at (160-220)°C for dehydration and esterification, and the acid value is detected to be 70mgKOH / g, and the temperature is reduced to obtain a polycondensation oligomer; 5.78g potassium carbonate is added to the mixture and reacted to ≤1mgKOH / g. The water and aromatic hydrocarbons are distilled off under reduced pressure, and 16.29g ethyl 2-isocyanoacrylate is added, and the reaction is carried out at 30-60°C for 1-5h to prepare the macromonomer M005.

[0084] The photocurable anti-fog coating is prepared as follows: monomers, photocurable resin, solvent, photoinitiator and auxiliary agent are taken respectively by weight, stirred and mixed to obtain the anti-fog coating.

[0085] Example 6

[0086] The present application provides a photocurable anti-fog coating, comprising 8 g of monomer, 30 g of photocurable resin, 60 g of solvent, 0.8 g of photoinitiator and 0.03 g of auxiliary agent;

[0087] In this embodiment, the monomers include pentaerythritol triacrylate, (9) ethoxylated trimethylolpropane triacrylate and dipentaerythritol hexaacrylate in a mass ratio of 3:2:2; the photoinitiator is 1-hydroxy-cyclohexyl phenyl ketone and 2,4,6-trimethylbenzoyl-diphenylphosphine oxide in a mass ratio of 3:1; the auxiliary agent is a leveling agent, and the leveling agent is a commercially available polyether-modified silicone leveling agent; the solvent includes isopropanol, n-butanol, butanone and propylene glycol methyl ether in a mass ratio of 6:3:1:2.

[0088] Photocurable resin has a comb-like polymer with a hydrophobic long carbon chain main chain, hydrophilic functional group side chains and double bonds. The hydrophilic functional groups on the side chains in the photocurable resin are far away from the main chain, that is, the hydrophilic anions in the side chains will not be too close to the main chain structure, so that the coating can obtain excellent anti-fog effect and water resistance effect.

[0089] The preparation of the photocurable resin is as follows: take 100g of comb polymer B006 and 14.36g of isophorone diisocyanate to react at 50±5°C, detect the NCO content to determine the degree of reaction, continue to add 9.31g of hydroxypropyl methacrylate, add 50ppm of p-hydroxyanisole and 100ppm of dibutyltin dilaurate, raise the temperature to 70°C, continue the reaction, and detect the NCO content to determine the reaction endpoint.

[0090] The preparation of the comb-like polymer is as follows: 55g of the macromonomer M006, 20g of methyl methacrylate, 10g of isobornyl methacrylate, 15g of hydroxyethyl acrylate and 1.0g of dibenzoyl peroxide are mixed for later use, 70g of ethyl acetate and 30g of butanone are put into a reactor, heated and stirred to (60-90)°C, a mixture of the monomer and the initiator is added dropwise for (3-5)h, the mixture is kept warm for (3-5)h, and the material is cooled and discharged to obtain a comb-like polymer B006.

[0091] The preparation of the macromonomer is as follows: 100g 12-hydroxylauric acid and 5g xylene are mixed, refluxed at (160-220)°C for dehydration and esterification, and the acid value is detected to be 60mgKOH / g, and the temperature is lowered to obtain a polycondensation oligomer; 13.82g potassium hydroxide is added to the mixture and reacted to ≤1mgKOH / g. The water and aromatic hydrocarbons are distilled off under reduced pressure, and 15.51g 2-isocyanoethyl methacrylate is added, and the reaction is carried out at 30-60°C for 1-5h to prepare the reaction monomer M006.

[0092] The photocurable anti-fog coating is prepared as follows: monomers, photocurable resin, solvent, photoinitiator and auxiliary agent are taken respectively by weight, stirred and mixed to obtain the anti-fog coating.

[0093] Example 7

[0094] The present application provides a photocurable anti-fog coating, comprising 8 g of monomer, 30 g of photocurable resin, 60 g of solvent, 0.8 g of photoinitiator and 0.03 g of auxiliary agent;

[0095] Among them, the monomers in this embodiment include trimethylolpropane triacrylate, pentaerythritol triacrylate and dipentaerythritol hexaacrylate in a mass ratio of 4:3:1; the photoinitiator is 1-hydroxy-cyclohexyl phenyl ketone and 2,4,6-trimethylbenzoyl-diphenylphosphine oxide in a mass ratio of 3:1; the auxiliary agent is a leveling agent, and the leveling agent is a commercially available polyether-modified silicone leveling agent; the solvent includes isopropyl alcohol, butanone and propylene glycol methyl ether in a mass ratio of 6:1:5.

[0096] Photocurable resin has a comb-like polymer with a hydrophobic long carbon chain main chain, hydrophilic functional group side chains and double bonds. The hydrophilic functional groups on the side chains in the photocurable resin are far away from the main chain, that is, the hydrophilic anions in the side chains will not be too close to the main chain structure, so that the coating can obtain excellent anti-fog effect and water resistance effect.

[0097] The preparation of the photocurable resin is as follows: take 100g of comb polymer B007 and 16.23g of isophorone diisocyanate to react at 50±5°C, detect the NCO content to determine the degree of reaction, continue to add 8.48g of hydroxyethyl acrylate, add 50ppm of p-hydroxyanisole and 100ppm of dibutyltin dilaurate, raise the temperature to 70°C, continue the reaction, and detect the NCO content to determine the reaction endpoint.

[0098] The preparation of the comb-like polymer is as follows: 55 g of the macromonomer M007, 11 g of methyl methacrylate, 15 g of isobornyl methacrylate, 19 g of hydroxyethyl methacrylate and 1.0 g of dibenzoyl peroxide are mixed for later use, 70 g of ethyl acetate and 30 g of butanone are added into a reactor, heated and stirred to (60-90) ° C, a mixture of the monomer and the initiator is added dropwise for (3-5) h, the mixture is kept warm for (3-5) h, and the material is cooled and discharged to obtain a comb-like polymer B007.

[0099] The preparation of the macromonomer is as follows: 100g 12-hydroxystearic acid and 5g xylene are mixed, refluxed at (160-220)°C for dehydration and esterification, the acid value is detected to be 50mgKOH / g, and the temperature is reduced to obtain a polycondensation oligomer; 3.15g lithium carbonate is added to the mixture and reacted to ≤1mgKOH / g. The water and aromatic hydrocarbons are distilled off under reduced pressure, 16.96g 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.

[0100] The photocurable anti-fog coating is prepared as follows: monomers, photocurable resin, solvent, photoinitiator and auxiliary agent are taken respectively by weight, stirred and mixed to obtain the anti-fog coating.

[0101] Table 1 Addition amount of each component of macromonomer in Examples 1-7

[0102]

[0103]

[0104] Table 2 Addition amount of each component of comb polymer in Examples 1-7

[0105]

[0106]

[0107] Table 3 Addition amount of each component of photocurable resin in Examples 1-7

[0108]

[0109]

[0110] Table 4 Addition amount of each component of anti-fog coating of Examples 1-7

[0111]

[0112]

[0113] Use air spraying method, pre-bake at (60-70)℃ for (3-5)min on PC, then enter the UV curing equipment, the light curing energy is (600-800)mJ / cm 2 , coating thickness (1-5) μm.

[0114] The test method is as follows:

[0115] 1. Adhesion: According to GB / T 9286-2021, 100 grid tests with 1mm spacing tape.

[0116] 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 fogging after 10 seconds.

[0117] 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.

[0118] 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 carried out.

[0119] 5. Anti-fog durability: Repeat the anti-fog test 10 times in a row, dry naturally at room temperature for 1 hour each time, and the anti-fog performance can still meet the requirements after 10 times.

[0120] The anti-fog coatings prepared in Examples 1-7 were tested, and the specific results are shown in the following table:

[0121]

[0122]

[0123] 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. A light-curing anti-fog coating, characterized in that: The invention comprises the following raw materials in parts by weight: 30 parts of light-curing resin; 8 parts of monomer; 60 parts of solvent; 0.8 parts of photoinitiator; 0.03 parts of additives; The photocurable resin is a polymer having a hydrophobic long carbon chain main chain, a hydrophilic functional group side chain and a double bond.

2. The photocurable anti-fog coating according to claim 1, characterized in that: The photocurable resin is prepared as follows: a comb-like polymer is reacted with isophorone diisocyanate at 50±5° C., the NCO content is detected to determine the degree of reaction, an acrylate monomer containing a hydroxyl group is added, the temperature is increased, the reaction is continued, and the NCO content is detected to determine the end point of the reaction.

3. The photocurable anti-fog coating according to claim 2, characterized in that: The comb polymer comprises the following raw materials in parts by weight: 38-55 parts of macromonomer; 45-62 parts of reactive monomer; 100 parts of solvent; Initiator 0.5-1 part; The reactive monomers include linear, branched or cyclic alkyl acrylates and hydroxyl-containing acrylate monomers.

4. The photocurable anti-fog coating according to claim 3, characterized in that: The linear, branched or cyclic alkyl acrylate is selected from any one or more of methyl methacrylate, n-butyl (meth)acrylate, isooctyl (meth)acrylate and isobornyl methacrylate.

5. The photocurable anti-fog coating according to claim 3, characterized in that: The solvent is selected from any one or more of ethyl acetate, acetone, and butanone.

6. A light-curing anti-fog coating according to claim 2 or 3, characterized in that: The hydroxyl-containing acrylic acid ester monomer is selected from any one or more of hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, and hydroxybutyl (meth)acrylate.

7. The photocurable anti-fog coating according to claim 3, characterized in that: The macromonomer comprises the following raw materials in 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 500-1200, and the acid value of the polycondensation oligomer is 50-110; The anion reactant is selected from any one of bicarbonate, carbonate or monobasic base; The isocyanate acrylate monomer is selected from any one of 2-isocyanoethyl acrylate, 2-isocyanoethyl methacrylate, and 2-(2-isocyanatoethoxy)ethyl methacrylate.

8. The photocurable anti-fog coating according to claim 2, characterized in that: During the preparation of the photocurable resin, auxiliary agents are added, and the auxiliary agents include catalysts and inhibitors.

9. The photocurable anti-fog coating according to claim 1, characterized in that: The monomer is selected from any one or more of trimethylolpropane triacrylate (TMPTA), pentaerythritol triacrylate (PETA), ethoxylated trimethylolpropane triacrylate (EO9TMPTA), and dipentaerythritol hexaacrylate (DPHA).

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