A waterborne modified fluorosilicone resin coating composition, coating and method of making the same

Abstract

The application discloses a kind of water-based modified fluorosilicone resin coating compositions and the preparation method of coating layer.For this, amino epoxy modified fluorosilicone resin EAFSi emulsion is combined with water-based nano flame-retardant slurry, anti-flash rust agent, defoaming agent, bactericide to form A material;Water-based epoxy resin ER-B and water-based nano flame-retardant slurry, anti-flash rust agent, defoaming agent, bactericide are combined to form B material.When using, A, B material is mixed according to proportion again using modified organic amine curing agent is adjusted to make the molar ratio of system N-H bond and epoxy group 1-1.1:1, so that the coating composition and coating layer prepared, can have good adhesion of epoxy resin again can show the performance of anti-fouling, salt fog resistance, flame-retardant and the like of flame-retardant fluorosilicone coating layer.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of functional coatings and layers, and specifically relates to a preparation method of a water-based fluorosilicon resin emulsion coating composition and layer based on amino silane ring-opening epoxy resin modification. BACKGROUND

[0002] In recent years, affected by environmental protection policies, water-based resin coatings and coatings are favored and have become the development direction and mainstream today. It is well known that fluorosilicon resin has excellent water and oil repellency and is widely used in functional anticorrosion coatings, superhydrophobic interface construction, electronic packaging, etc. [Qiufeng An, Zhunjun Lv, Wenchao Shangguan, et al. Coatings [J]. 2018, (8) (3): 100-107; Ge Ping. Master's thesis [D], Shaanxi University of Science and Technology, 2022; Xiaojing Guo, Chaohua Xue, Shuntian Jia, et al. Chemical Engineering Journal, 2017, 320: 330-341], but most of the fluorosilicon resin coatings on the market are solvent products, which not only leads to high prices and unpleasant odor of such coatings, seriously affecting the application and promotion of such coatings, and therefore there is an urgent need for water-based fluorosilicon resin coatings with no odor or low odor, suitable price and high cost performance to meet market demand.

[0003] Emulsion polymerization is a common means to implement water-based organic (fluoro) silicon resin polymerization reaction, so can we use a method similar to emulsion polymerization to synthesize water-based fluorosilicon resin emulsion with water and oil repellency, and use it for the preparation of functional coatings and coatings such as flame retardant and anticorrosion? It is of great concern. In addition, it is known from the literature that the stronger the water and oil repellency of fluorosilicon resin, the worse the adhesion of the coating prepared based on the resin. Based on this, can we use a strong adhesive amino silane ring-opening modified epoxy resin as a reactive adhesion promoter component, and then hydrolysis and polycondensation of fluorocarbon silane, amino silane, etc. to synthesize modified water-based fluorosilicon resin emulsion, so that the target fluorosilicon resin can not only improve the adhesion of the coating, but also make the coating composition and coating prepared based on the new modified fluorosilicon resin emulsion + nano flame retardant slurry also have good surface hydrophobic and oleophobic properties, flame retardancy and mechanical strength, but there are few research reports. SUMMARY

[0004] In view of the lack of water-based fluorosilicon resin emulsion coatings on the market and the poor adhesion of fluorosilicon resin coatings, the present application discloses a preparation method of a functional composite coating composition and coating prepared based on a fluorosilicon resin water-based emulsion modified by an amino silane ring-opening epoxy resin.

[0005] To this end, the present application adopts the following technical solutions:

[0006] A method for preparing a waterborne modified fluorosilicone resin coating composition, characterized in that the coating is composed of A and B materials; the A material is composed of 100 parts of amino silane ring-opening modified fluorosilicone resin (EAFSi, referred to as amino epoxy modified fluorosilicone resin) emulsion with a solid content of about 25-30%, 50-80% of waterborne nano flame-retardant slurry with a solid content of about 70-75% based on the solid content of the modified fluorosilicone resin (EAFSi), 0.5-1.0 parts of anti-fouling agent for waterborne coatings, 0.1-0.3 parts of defoaming agent for waterborne coatings, and 0.1-2.0 parts of bactericide.

[0007] The B material is composed of 100 parts of waterborne epoxy resin (ER-B) emulsion with a solid content of about 40-60%, 50-80% of waterborne nano flame-retardant slurry with a solid content of about 70-75% based on the solid content of the epoxy resin ER-B, 0.5-1.0 parts of anti-fouling agent for waterborne coatings, 0.1-0.3 parts of defoaming agent for waterborne coatings, and 0.1-2.0 parts of bactericide. For convenience, the B material should be diluted to the same solid content as A before use.

[0008] The amino epoxy modified fluorosilicone resin [EAFSi, structure see formula (1)] emulsion is a copolymer emulsion formed by amino silane (ASi-1) ring-opening modified epoxy resin [EASi, see formula (2)] and alkyl silane (RSi) or / and phenyl silane (PSi) and fluorocarbon silane (RSi) and amino silane (ASi-2) in an aqueous phase by emulsion hydrolysis and polycondensation, with a solid content of about 25-30% and NH bond content of about 0.01%-0.1% based on the number of moles of N-H bond contained in 100 g of emulsion. f Si) and amino silane (ASi-2) in an aqueous phase by emulsion hydrolysis and polycondensation, with a solid content of about 25-30% and NH bond content of about 0.01%-0.1% based on the number of moles of N-H bond contained in 100 g of emulsion.

[0009]

[0010] Formula (1) is the structural formula of the main component of EAFSi resin, wherein AFSi is the structural fragment of amino-containing fluorosilicone resin;

[0011]

[0012] Formula (2) is the structural formula of amino silane ring-opening modified epoxy resin (EASi).

[0013] The main component of the amino epoxy modified fluorosilicone resin (EAFSi) emulsion is a fluorosilicone copolymer containing D (i.e. -SiO 2 / 2 -) and T (i.e. -SiO 3 / 2 -) type siloxane linkages in the structure, such as EASi-co-amino hydrocarbyl siloxane-co-fluorocarbon siloxane-co-C 1-18alkyl(methyl)siloxane and / or (methyl)phenylsiloxane, EASi-co-aminoalkyl(methyl)siloxane-co-fluoroalkylsiloxane-co-C 1-18 alkyl(methyl)siloxane and / or (methyl)phenylsiloxane, EASi-co-aminoalkyl(methyl)siloxane-co-fluoroalkylsiloxane-co-C 1-18 alkyl(methyl)siloxane and / or (methyl)phenylsiloxane, EASi-co-aminoalkyl(methyl)siloxane-co-fluoroalkylsiloxane-co-C 1-18 alkyl(methyl)siloxane and / or (methyl)phenylsiloxane, EASi-co-aminoalkyl(methyl)siloxane-co-fluoroalkylsiloxane-co-C 1-18 alkyl(methyl)siloxane and / or (methyl)phenylsiloxane, EASi-co-aminoalkyl(methyl)siloxane-co-fluoroalkylsiloxane-co-C 1-18 alkyl(methyl)siloxane and / or (methyl)phenylsiloxane, EASi-co-aminoalkyl(methyl)siloxane-co-fluoroalkylsiloxane-co-C 1-18 alkyl(methyl)siloxane and / or (methyl)phenylsiloxane, EASi-co-aminoalkyl(methyl)siloxane-co-fluoroalkylsiloxane-co-C 1-8 perfluoroalkylethyl, perfluoroaryl, perfluoropolyether group, or 2-3 kinds thereof; said C 1-18 alkyl is one or 2-3 kinds of normal alkyl, isoalkyl or cycloalkyl having 1-18 carbon atoms in the structure.

[0014] The EAF Si resin main component is preferably selected from EASi-co-(γ-aminopropyl) siloxane-co-heptadecafluorooctylethylsiloxane-co-dimethylsiloxane-co-diphenylsiloxane, EASi-co-(γ-aminopropyl)methylsiloxane-co-heptadecafluorooctylethylsiloxane-co-dimethylsiloxane-co-phenylsiloxane, EASi-co-(γ-aminopropyl)siloxane-co-tridecafluorohexylethylsiloxane-co-dimethylsiloxane-co-diphenylsiloxane, EASi-co-(γ-aminopropyl)siloxane-co-tridecafluorohexylethylsiloxane-co-dimethylsiloxane-co-phenylsiloxane, EASi-co-(γ-aminopropyl)methylsiloxane-co-tridecafluorohexylethylsiloxane-co-diphenylsiloxane, EASi-co-(γ-aminopropyl)siloxane-co-tridecafluorohexylethylsiloxane-co-diphenylsiloxane, EASi-co-(γ-piperazinopropyl)methylsiloxane-co-perfluorooctylethylsiloxane-co-dimethylsiloxane-co-phenylsiloxane, EASi-co-(γ-piperazinopropyl)methylsiloxane-co-perfluorooctylethylsiloxane-co-methylsiloxane-co-diphenylsiloxane, EASi-co-(γ-piperazinopropyl)methylsiloxane-co-heptadecafluorooctylethylsiloxane-co-cyclohexylmethylsiloxane-co-phenylsiloxane, EASi-co-(γ-piperazinopropyl)methylsiloxane-co-heptadecafluorooctylethylsiloxane-co-cyclohexylsiloxane-co-diphenylsiloxane; EASi-co-(γ-piperazinopropyl)methylsiloxane-co-heptadecafluorooctylethylsiloxane-co-C 8-18 alkylsiloxane-co-diphenylsiloxane, EASi-co-(γ-piperazinopropyl)methylsiloxane-co-heptadecafluorooctylethylsiloxane-co-C 8-18 alkylsiloxane, EASi-co-(γ-piperazinopropyl)methylsiloxane-co-heptadecafluorooctylethylsiloxane-co-C 8-18alkylsiloxane-co-cyclohexylmethylsiloxane, EASi-co-(gamma-piperazinylpropyl)methylsiloxane-co-heptadecafluorooctylethylsiloxane-co-cyclohexylsiloxane-co-(di)phenylsiloxane, EASi-co-(N,N-dimethyl-gamma-aminopropyl-gamma-aminopropyl)methylsiloxane-co-tridecafluorohexylethylsiloxane-co-dimethylsiloxane-co-diphenylsiloxane, EASi-co-(N,N-dimethyl-gamma-aminopropyl-gamma-aminopropyl)siloxane-co-tridecafluorohexylethylsiloxane-co-dimethylsiloxane-co-diphenylsiloxane, EASi-co-(N,N-dimethyl-gamma-aminopropyl-gamma-aminopropyl)methylsiloxane-co-tridecafluorohexylethylsiloxane-co-cyclohexylsiloxane-co-diphenylsiloxane, EASi-co-(N,N-dimethyl-gamma-aminopropyl-gamma-aminopropyl)siloxane-co-tridecafluorohexylethylsiloxane-co-dimethylsiloxane-co-diphenylsiloxane, EASi-co-(N,N-dimethyl-gamma-aminopropyl-gamma-aminopropyl)methylsiloxane-co-tridecafluorohexylethylsiloxane-co-cyclohexylsiloxane-co-diphenylsiloxane, EASi-co-(N,N-dimethyl-gamma-aminopropyl-gamma-aminopropyl)siloxane-co-tridecafluorohexylethylsiloxane-co-dimethylsiloxane-co-diphenylsiloxane, EASi-co-(N-beta-aminopropyl-gamma-aminopropyl)methylsiloxane-co-tridecafluorohexylethylsiloxane-co-methylcyclohexylsiloxane-co-phenylsiloxane, EASi-co-(N-beta-aminopropyl-gamma-aminopropyl)methylsiloxane-co-tridecafluorohexylethylsiloxane-co-methylcyclohexylsiloxane-co-diphenylsiloxane, EASi-co-gamma-piperazinylpropylmethylsiloxane-co-isobutylsiloxane-co-diphenylsiloxane-co-heptadecafluorooctylethylsiloxane, EASi-N,N-dimethyl-gamma-aminopropyl-gamma-aminopropylmethylsiloxane-co-dodecylsiloxane-co-cyclohexylmethylsiloxane-co-tridecafluorohexylethylsiloxane-co-perfluoropolyether-siloxane, EASi-co-gamma-aminopropylmethylsiloxane-co-diethylsiloxane-co-hexadecylmethylsiloxane-co-phenylsiloxane-co-pentafluorophenylsiloxane, and the like; said EASi being the product of the aminolysis ring-opening reaction of an epoxy resin ER-A with an aminosilane ASi-1 in a silane medium, an aminosilane ring-opening epoxy resin.

[0015] The aqueous aminofunctional fluorosilicone resin (EAFSi) emulsion can be prepared by the following two steps:

[0016] (1) Synthesis of adhesion promoter component, aminosilane ring-opening modified epoxy resin (EASi)

[0017] The epoxy resin (ER-A) and the aminosilane (ASi-1) were weighed according to the molar ratio of epoxy group in the epoxy resin (ER-A) to the amino group in the aminosilane (ASi-1) of about 1:1-1.1, respectively;

[0018] The amino silane ASi-1 is mixed with about 100-150% of the subsequent reaction raw material alkyl silane (RSi) or / and phenyl silane (PSi) by mass fraction of (ER-A+ASi-1), then heated to 40-60℃, and then (drop) added with the epoxy resin ER-A, and the reaction temperature is controlled at 40-60℃ for 30-60min to carry out the aminolysis ring-opening reaction, so that the ER-A reacts with the ASi-1 in the silane RSi or / and PSi medium and is converted into the amino silane ASi-1 ring-opening modified epoxy resin (EASi); after the reaction is completed, a transparent liquid is obtained, which is a solution formed by dispersing the EASi in the silane RSi or / and PSi medium, denoted as A', and the EASi content is about 40-50% by mass fraction of EASi in A' (i.e. the total mass of EASi+RSi or / and PSi).

[0019] (2) Preparation of an amino epoxy modified fluorosilicon resin aqueous emulsion

[0020] Take an appropriate amount of A', and add RSi or / and PSi, fluorocarbon group silane (RSi), amino silane (ASi-2) to A' according to the mass of EASi, RSi or / and PSi contained in A' so that the mass ratio of EASi:(RSi or / and PSi):RSi:ASi-2 in the system is about 5-10:40-75:10-30:10-20, and mix well. The obtained mixture is denoted as M. f Si), amino silane (ASi-2) to A' according to the mass of EASi, RSi or / and PSi contained in A' so that the mass ratio of EASi:(RSi or / and PSi):RSi:ASi-2 in the system is about 5-10:40-75:10-30:10-20, and mix well. The obtained mixture is denoted as M. f Si), amino silane (ASi-2) to A' according to the mass of EASi, RSi or / and PSi contained in A' so that the mass ratio of EASi:(RSi or / and PSi):RSi:ASi-2 in the system is about 5-10:40-75:10-30:10-20, and mix well. The obtained mixture is denoted as M.

[0021] In a reaction bottle with a thermometer, a stirrer, and a reflux condenser, 5-10% of an anionic / nonionic surfactant by mass of M is added, dissolved in water to form a transparent aqueous solution, the system pH is adjusted to 9-10, then heated to the set reaction temperature of 60-80℃, and then M is added dropwise, the dropwise addition speed is controlled so that it is completed within 1-2h, then it is incubated at 60-80℃ for 6-10h, and then cooled to room temperature, the gel is filtered out with a 200 mesh gauze, and then rotary evaporation is performed for about 30min to remove low boiling byproduct small molecule alcohol, a white emulsion with blue fluorescence is obtained, which is an amino epoxy modified fluorosilicon resin aqueous emulsion, denoted as EAFSi, and the solid content is about 25-30%, and the NH content in the emulsion is about 0.01%-0.1% by mole number of N-H bonds contained in 100g of the resin emulsion.

[0022] In the above synthesis step, the epoxy resin ER-A is an aromatic, aliphatic or alicyclic epoxy resin having 1 to 2 epoxy groups at each molecular end, an epoxy value of about 0.2 to 0.59 in terms of the number of moles of epoxy groups contained in 100 g of the resin, and a viscosity of about 500 to 20,000 mPa-s, and one of a bisphenol A epoxy resin (e.g., E51, E44, E20), a hydrogenated bisphenol A epoxy resin (e.g., HE44), a glycidyl ether type epoxy resin, a glycidyl ester type epoxy resin, a linear aliphatic epoxy resin, or an alicyclic epoxy resin is selected.

[0023] The amino silane ASi-1 and ASi-2, which can be the same or different, is a silane containing primary and secondary amino groups and 2-3 alkoxy groups in the molecule, selected from γ-aminopropyl trialkoxysilane (such as γ-aminopropyl trimethoxysilane, γ-aminopropyl triethoxysilane), γ-aminopropyl methyl dialkoxysilane (such as γ-aminopropyl methyl dimethoxysilane, γ-aminopropyl methyl diethoxysilane), n-n-butyl-γ-aminopropyl trialkoxysilane (such as n-n-butyl-γ-aminopropyl trimethoxysilane), n-n-butyl-γ-aminopropyl methyl dialkoxysilane (such as n-n-butyl-γ-aminopropyl methyl dimethoxysilane), N-cyclohexyl-γ-aminopropyl methyl dialkoxysilane (such as N-cyclohexyl-γ-aminopropyl methyl dimethoxysilane, N-cyclohexyl-γ-aminopropyl methyl diethoxysilane), N-cyclohexyl-γ-aminopropyl trialkoxysilane (such as N-cyclohexyl-γ-aminopropyl trimethoxysilane, N-cyclohexyl-γ-aminopropyl triethoxysilane), N-β-aminoethyl-γ-aminopropyl trialkoxysilane [such as N-β-aminoethyl-γ-aminopropyl trimethoxysilane (KH-792), N-β-aminoethyl-γ-aminopropyl triethoxysilane], N-β-aminoethyl-γ-aminopropyl methyl dialkoxysilane [such as N-β-aminoethyl-γ-aminopropyl methyl dimethoxysilane (KH-602), N-β-aminoethyl-γ-aminopropyl methyl diethoxysilane], N,N-dimethyl-γ-aminopropyl-γ-aminopropyl trialkoxysilane (such as N,N-dimethyl-γ-aminopropyl-γ-aminopropyl trimethoxysilane, N,N-dimethyl-γ-aminopropyl-γ-aminopropyl triethoxysilane), N,N-dimethyl-γ-aminopropyl-γ-aminopropyl methyl dialkoxysilane [such as N,N-dimethyl-γ-aminopropyl-γ-aminopropyl methyl dimethoxysilane (KH-121), N,N-dimethyl-γ-aminopropyl-γ-aminopropyl methyl diethoxysilane], γ-piperazinyl propyl methyl dialkoxysilane [such as γ-piperazinyl propyl methyl dimethoxysilane (GP-108), γ-piperazinyl propyl methyl diethoxysilane], γ-piperazinyl propyl trialkoxysilane (such as γ-piperazinyl propyl trimethoxysilane, γ-piperazinyl propyl triethoxysilane), 2,2,6,6-tetramethylpiperidyl-4-oxy propyl methyl dialkoxysilane (such as 2,2,6,6-tetramethylpiperidyl-4-oxy propyl methyl dimethoxysilane, 2,2,6,6-tetramethylpiperidyl-4-oxy propyl methyl diethoxysilane), and the like, wherein the alkoxy group is methoxy or ethoxy.

[0024] The alkyl silane (RSi) is a silane containing 1-2 C 1-18 alkyl groups and 2-3 alkoxy groups in the structure, selected from C 1-18 alkyl trialkoxysilane (including C 1-18 alkyl trimethoxysilane and C1-18 alkyltriethoxysilane), C 1-18 Alkylmethyldialkoxysilanes (including C 1-18 Alkylmethyldimethoxysilane, C 1-18 Alkylmethyldiethoxysilane), diethyldimethoxysilane, diethyldiethoxysilane, C 5-6 Cycloalkylmethyldialkoxysilanes (such as cyclopentylmethyldimethoxysilane, cyclopentylmethyldiethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane), C 5-6 One or two to three of the following cycloalkyltrialkoxysilanes (such as cyclopentyltrimethoxysilane, cyclopentyltriethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, etc.), wherein the alkoxy groups are as described above.

[0025] The phenylsilane (PSi) mentioned above is a silane containing 1-2 phenyl groups and 2-3 alkoxy groups in its structure, and is selected from one or two of phenyltrialkoxysilane (such as phenyltrimethoxysilane, phenyltriethoxysilane), methylphenyldialkoxysilane (such as methylphenyldimethoxysilane, methylphenyldiethoxysilane), and diphenyldialkoxysilane (such as diphenyldimethoxysilane, diphenyldiethoxysilane).

[0026] The fluorocarbon-based silane (R) f Si), where a molecule has one carbon atom attached. 1-8 Silanes with perfluoroalkyl ethyl, perfluoroaryl, or perfluoropolyether groups further connected to 2-3 alkoxy groups, selected from C 1-8 Perfluoroalkyl ethyltrialkoxysilanes (such as C 1-8 Perfluoroalkyl ethyltrimethoxysilane and C 1-8 Perfluoroalkyl ethyltriethoxysilane), C 1-8 Perfluoroalkyl ethylmethyl diekoxysilanes (such as C 1-8 Perfluoroalkyl ethyl methyl dimethoxysilane and C 1-8one or a mixture of two to three of perfluoroalkyl ethyl methyl diethoxysilane, perfluorophenyl trialkoxysilane (such as perfluorophenyl trimethoxysilane, perfluorophenyl triethoxysilane), perfluorophenyl methyl dialkoxysilane (such as perfluorophenyl methyl dimethoxysilane, perfluorophenyl methyl diethoxysilane), 3-heptafluoroisopropoxy propyl trialkoxysilane (such as 3-heptafluoroisopropoxy propyl trimethoxysilane, 3-heptafluoroisopropoxy propyl triethoxysilane), perfluoropolyether group trialkoxysilane with an average molecular weight Mn = 500-1000 (such as perfluoropolyether group trimethoxysilane with Mn = 500-1000, perfluoropolyether group triethoxysilane with Mn = 500-1000), perfluoropolyether group methyl dialkoxysilane with Mn = 500-1000 (such as perfluoropolyether group methyl dimethoxysilane with Mn = 500-1000, perfluoropolyether group methyl diethoxysilane with Mn = 500-1000), and the like. 1-8 The perfluoroalkyl group includes heptadecafluorooctyl, tridecafluorohexyl, nonafluorobutyl, trifluoropropyl, and the like, and the alkoxy group is methoxy and ethoxy.

[0027] The anionic / nonionic surfactant is a mixture of anionic surfactant and nonionic surfactant, and the mass ratio of the two is anionic: nonionic surfactant = 1:1-3; the nonionic surfactant is selected from one of fluorocarbon alkyl polyoxyethylene ether with an EO number of about 3-25, fatty alcohol polyoxyethylene ether, alkyl phenol polyoxyethylene ether, fatty acid polyoxyethylene ether ester, and fatty acid sorbitan polyoxyethylene ether ester, and the preferred nonionic surfactant is one or more of isomeric tridecanol polyoxyethylene ether such as 1350, 1370, 1390, 13100, 13120, or isomeric decanol polyoxyethylene ether such as XL-30, XL-70, XL-90, XP-30, XP-90, and the like; the anionic surfactant is selected from one of isomeric fatty alcohol polyoxyethylene ether sodium sulfate (AES), sodium perfluorooctyloxybenzenesulfonate (FBS), sodium perfluoropolyether carboxylate with an average molecular weight Mn = 1000 (PFPE-AC-1000), fatty alcohol polyoxyethylene ether carboxylate (AEC), sodium secondary alkyl sulfonate (SAS), sodium dodecyl sulfate (SDS, K12), or potassium dodecyl sulfate, and the like.

[0028] The aqueous nano flame-retardant slurry is a uniform dispersion of inorganic nano powder containing a flame retardant dispersed in water under the action of a coating additive (such as a defoaming agent, a leveling agent, a dispersant, and the like) and a sand mill, and the average particle size of the nano particles in the slurry is ≤25 μm, and the solid content is about 70-75%, which is ordered or commissioned from a relevant manufacturer such as Shaanxi Baotaoshan Paint Co., Ltd.

[0029] The inorganic nano-powder containing flame retardant is a composite of inorganic nano-TiO2, zinc oxide, calcium carbonate, ferroferric oxide, aluminum oxide, etc. and a flame retardant such as aluminum hydroxide or magnesium hydroxide, etc. in a mass ratio of 1:1-3.

[0030] The anti-fretting agent is FA179 of Haimins or R-765 of Tianjin Qikai Chemical Industry; the defoaming agent for water-based paint is Tego 810 defoaming agent produced by Degussa Company; and the bactericide is an isothiazolone (also known as Kathon) bactericide and water-soluble nano-silver widely used in water-based paint systems.

[0031] The emulsion containing water-based epoxy resin (ER-B) used in the B material is mainly composed of bisphenol A epoxy resin or hydrogenated bisphenol A epoxy resin, which can be the same as or different from the epoxy resin ER-A used in the EASi synthesis step, has a solid content of about 40-60%, an epoxy group content of about 0.20-0.25 in terms of the number of moles of epoxy groups contained in 100 g of the emulsion, and a viscosity of about 800-1500 mPa.s. It is a stable emulsion formed by emulsifying (hydrogenated) bisphenol A epoxy resin (such as E51 or E44, HE44, etc.) in water under the action of a non-ionic reactive epoxy polyether modified epoxy resin emulsifier. It can be obtained by directly emulsifying (hydrogenated) bisphenol A epoxy resin + 20-30% epoxy polyether modified epoxy resin emulsifier in water under high-speed stirring of a high-shear emulsifier, or ordered from relevant manufacturers such as Balin Petrochemical Company. The non-ionic epoxy polyether modified epoxy resin emulsifier used is DY-56 emulsifier produced by Shenyang Dongyang Paint and Decoration Co., Ltd. or CYDW-102 produced by Balin Petrochemical Company.

[0032] The preparation method of the water-based amino-epoxy modified fluorosilicon resin coating includes two steps of paint preparation and coating preparation.

[0033] (1) Paint preparation: take A and B materials diluted to the same solid content, mix them uniformly according to the mass ratio of A:B = 1-2:1 (wt / wt), then adjust the components with a water-based epoxy curing agent, i.e. a modified organic amine, so that the molar ratio of N-H bond in the system (A + adjusting agent) to epoxy group in the B material is about 1-1.1:1, mix and stir uniformly, vacuum degassing, and obtain a uniform mixture, which is the paint working solution.

[0034] (2) Coating preparation

[0035] Bottom coating treatment: take a metal substrate after sand blasting treatment (which can remove impurities or rust marks attached to the surface of the substrate, increase the roughness and cleanliness of the substrate surface), first spray a layer of primer coating with a thickness of about 20-25 μm based on a water-based epoxy zinc-rich primer and a curing agent on the surface, and cure at room temperature for 2-3 h. The surface-dried coating obtained is used as the bottom coating sample (DC) of the present application.

[0036] Modified fluorosilicon surface layer: the DC primer sample is fixed on the spray sample table, the working solution of the coating of the present application is uniformly sprayed on the surface of the DC coating layer by using a spray gun, the spraying amount is controlled so that the thickness of the dry surface layer is about 25-30 μm, it is leveled at room temperature for 20-30 min, then it is baked at 70-80℃ for 30-60 min to remove the water in the coating, then it is heated to 120-150℃ and solidified for 30-60 min, the obtained coating sample is the coating sample prepared based on the amino-epoxy modified fluorosilicon resin water-based coating composition.

[0037] The water-based epoxy resin curing adjusting component is an emulsion obtained by emulsifying the end group type PA-ER-PA product formed by ring-opening of epoxy resin (ER) and polyvalent organic amine (PA, such as diethylene triamine, triethylene tetramine, polyether amine such as D230, D400, etc.) and then emulsifying in water, the solid content is about 50-80%, it is processed by commissioning Balin Petrochemical or purchased from relevant manufacturers such as American Huntsman, and Aradur-38-1, ARAFUR series modified amine curing agent produced by Huntsman is preferentially selected.

[0038] The metal substrate is selected from one of tinplate, aluminum alloy, steel plate, copper-clad circuit board, etc.

[0039] The present application has the following advantages: the amino silane and epoxy resin are subjected to aminolysis ring-opening reaction in a solvent medium of the subsequent reaction raw material, i.e. alkyl silane RSi or / and aromatic hydrocarbon silane PSi, to synthesize an amino silane ring-opening epoxy resin (EASi) which has good adhesion and carries hydrolyzable groups, i.e. polyalkoxysilane groups, at the molecular end groups; then, without separation, the adhesion promoting component EASi is subjected to hydrolysis and co-condensation with fluorocarbon silane, alkyl silane and / or aromatic hydrocarbon silane, amino silane in an aqueous solution under the action of an anionic / non-ionic surfactant to obtain a water-based emulsion of a fluorosilicon resin (EAFSi) modified by the amino silane ring-opening epoxy resin, which can simplify the purification step of EASi synthesis and achieve the purpose of increasing the adhesion of the existing fluorosilicon resin and environmental protection. Secondly, by virtue of the characteristics that amino groups are easy to react with epoxy groups, the newly prepared water-based amino epoxy modified fluorosilicon resin emulsion is combined with water-based nano flame-retardant slurry, bactericide and the like to form a coating A component, a water-based epoxy resin ER-B emulsion + water-based nano flame-retardant slurry + bactericide and the like are combined to form a coating B component, then the two are compounded in a proportion and cured under the action of a modified organic amine curing regulator, the low surface energy hydrophobic and oleophobic fluorosilicon chain segments are cleverly utilized to enrich on the surface, and the Si-O backbone of the fluorosilicon resin main chain and the inorganic flame retardant are synergistically flame-retarded, so that the coating layer not only has the effects of adhesion, surface hydrophobicity, antifouling, salt mist resistance, impact resistance, flexibility and flame retardance, but also can reduce the traditional three-layer coating, i.e. epoxy zinc-rich primer + cloud iron epoxy mid-coat + fluorocarbon topcoat, to epoxy zinc-rich primer + modified fluorosilicon composite epoxy two-layer coating, thereby saving production cost and improving production efficiency. DETAILED DESCRIPTION

[0040] The present application is further described below in conjunction with examples, which are only used to explain the present application and are not a limitation on the protection scope of the present application.

[0041] (I) Preparation of water-based amino epoxy modified fluorosilicon resin emulsion

[0042] (1) Synthesis of adhesion promoting component, i.e. amino silane ring-opening modified epoxy resin (EASi)

[0043] According to the molar ratio of epoxy groups in epoxy resin (ER-A) to amino silane (ASi-1) of about 1:1-1.1, 20.0 g of epoxy resin ER-A with an epoxy value of about 0.2-0.59 and amino silane ASi-1 are respectively weighed.

[0044] The ASi-1 is mixed with about 100% by mass of the alkylsilane RSi or / and phenylsilane PSi, stirred and mixed uniformly, then placed in a three-necked flask equipped with a thermometer, reflux condenser and stirrer, heated to 40-60°C with stirring, and the above-mentioned epoxy resin ER-A is added (dropwise) while stirring, the reaction temperature is controlled at 40-60°C, and the stirring is continued for 30-60 min to allow the ER-A to undergo aminolysis ring-opening and conversion to an aminosilane ring-opening epoxy resin (EASi) in the medium of the subsequent reaction raw material silane RSi or / and PSi, to obtain a transparent liquid, denoted as A', which is a solution of the EASi dispersed in the medium of RSi or / and PSi. Depending on the different epoxy resins ER-A and aminosilanes ASi-1 used, the prepared series of EASi and the raw material usage are shown in Table 1.

[0045] Table 1 Synthesis of aminosilane-modified epoxy resin (EASi) precursors and raw materials

[0046]

[0047] * KH-550: γ-aminopropyltriethoxysilane; KH-554: γ-aminopropylmethyldimethoxysilane; KH-121: N,N-dimethyl-γ-aminopropyl-γ-aminopropylmethyldimethoxysilane; GP-108: γ-piperazinylpropylmethyldimethoxysilane; E51, E44, E20: bisphenol A epoxy resins E51, E44, E20 with epoxy values of 0.51, 0.44, 0.20, respectively; HE44: hydrogenated bisphenol A epoxy resin with an epoxy value of about 0.44.

[0048] (2) Preparation of an aminosilane-modified fluorosilicon resin (EAFSi) aqueous emulsion

[0049] EAFSi-1 is prepared using EASi-1 as an example.

[0050] Take 10.0 g of an EASi-1 solution with a solid content of about 50%, which contains 5.0 g of EASi-1, 2.5 g of DMDES and 2.5 g of DPDMS, then add 30.0 g of DMDES (total 32.5 g) and 30.0 g of DPDMS (total 32.5 g), 15.0 g of tridecafluorohexyl ethyl trimethoxysilane, and 15.0 g of γ-aminopropyltriethoxysilane KH-550 to the solution, the mass ratio of EASi-1:(DMDES and DPDMS):R f Si: KH-550 is about 5:65:15:15, stir and mix uniformly to obtain a total of 100.0 g of mixture, denoted as M, for standby use.

[0051] In a three-neck flask with thermometer, stirrer and reflux condenser, add 5% (about 5.0 g) of anionic / nonionic surfactant (1:1, wt / wt) consisting of 2.5 g of dodecylbenzenesulfonic acid (DBSA) and 2.5 g of isomeric tridecanol polyoxyethylene ether 1390, with 138.20 g of deionized water to form a transparent aqueous solution, then adjust the system pH to 9 with 10% NaOH, then stir and heat to the set reaction temperature 80°C, then add M dropwise, control the dropwise speed to complete in 2 h, then keep stirring at 80°C for 8 h, filter out the gel with a 200 mesh gauze, then remove the hydrolysis byproducts such as methanol and ethanol under the conditions of 60°C and P 表 =0.06 MPa to obtain a total of 243.10 g of emulsion with blue fluorescence, i.e. the main component is the aqueous emulsion of EASi-1-co-dimethylsiloxane-co-diphenylsiloxane-co-tridecafluorohexyl ethyl siloxane-co-(γ-aminopropyl) siloxane copolymer, i.e. the amino epoxy modified fluorosilicon resin (EAFSi-1) emulsion, the solid content is about 30.0% determined at 150°C for 30 min, and the NH bond content is about 0.0656 mol / 100 g in terms of the number of moles of N-H bonds contained in 100 g of resin emulsion.

[0052] The same operation as above is performed, using EASi-2 to EASi-4 in Table 1 instead of EASi-1, and changing the structures and amounts of alkylsilane RSi, arenesilane PSi, fluorocarbon silane R f Si and amino silane ASi-2, and the amino epoxy modified fluorosilicon resin FEASi-2 to -4 aqueous emulsion prepared by the same method and the amount of raw materials are shown in Table 2.

[0053] Table 2 List of raw materials for the synthesis of amino epoxy modified fluorosilicon resin aqueous emulsion

[0054]

[0055]

[0056] EAFSi-1: EASi-1-co-dimethylsiloxane-co-diphenylsiloxane-co-tridecafluoroheptyl ethyl siloxane-co-gamma-aminopropyl siloxane; EAFSi-2: EASi-2-co-isobutyl siloxane-co-diphenyl siloxane-co-heptadecafluorooctyl ethyl siloxane-co-gamma-piperazinyl propyl methyl siloxane; EAFSi-3: EASi-3-co-dodecyl siloxane-co-cyclohexyl methyl siloxane-co-tridecafluoroheptyl ethyl siloxane-co-perfluoropolyether siloxane-N,N-dimethyl-gamma-aminopropyl-gamma-aminopropyl methyl siloxane; EAFSi-4: EASi-4-co-diethyl siloxane-co-hexadecyl methyl siloxane-co-phenyl siloxane-co-pentafluorophenyl siloxane-co-gamma-aminopropyl methyl siloxane

[0057] (II) Examples

[0058] Example 1

[0059] (1) Preparation of the aqueous amino-epoxy modified fluorosilicone resin coating composition

[0060] Preparation of A1 material: Take 100.0 g of EAFSi-1 emulsion with a solid content of about 30.0%, and then add about 70% of water-based nano flame-retardant slurry TiO2 / Al(OH)3(mass ratio 1:1) with a solid content of about 75%, 0.5 g of anti-fouling agent FA-179 for water-based coatings, 0.1 g of Tego 810 defoamer from Degussa, and 0.2 g of 2-methyl-4-isothiazolin-3-one bactericide, mix well under stirring, and then vacuum degassing to obtain a total of 121.8 g of uniform fluid, which is A1 material, with a solid content of about 38.33% and an N-H content (calculated based on the number of moles of N-H bonds contained in 100 g of A material) of about 0.0539 mol / 100 g.

[0061] Preparation of B1 material: Take 100.0 g of water-based epoxy resin 102 / W50 (Baling Petrochemical Co., Ltd.) with a solid content of about 50% and an epoxy value of about 0.22, and then add about 70% of water-based nano flame-retardant slurry TiO2 / Al(OH)3(mass ratio 1:1) with a solid content of about 75%, 0.5 g of anti-fouling agent FA-179 for water-based coatings, 0.1 g of Tego 810 defoamer from Degussa, and 0.2 g of 2-methyl-4-isothiazolin-3-one bactericide, mix well under stirring to obtain 135.8 g of uniform fluid, which is B material, and then dilute with water to a solid content of about 38.33%, and an epoxy group content (calculated based on the number of moles of epoxy groups contained in 100 g of the coating) of about 0.1094 mol / 100 g, which is recorded as B1 material.

[0062] Preparation of waterborne amino epoxy modified fluorosilicon resin coating

[0063] Coating working solution preparation: 100 g of A1 material, 50.0 g of B1 material were weighed according to the mass ratio of A1:B1 of about 2:1, stirred and mixed uniformly, and adjusted with 1.18 g of Huntsman waterborne epoxy curing agent Aradur-38-1 with an ammonia value of 190, an active hydrogen equivalent of 150, and a solid content of 80% to make the molar ratio of N-H bond in A1+adjusting agent to epoxy group in B1 material about 1.1:1, stirred and mixed uniformly, vacuum degassing, and coating working solution was obtained.

[0064] Primer treatment: after sand blasting and cleaning treatment, the tinplate was sprayed with a primer composed of waterborne zinc-rich epoxy primer and curing agent (mass ratio 100:20, provided by Shaanxi Baotaoshan Paint Co., Ltd.) on the surface of the tinplate with a rock gun with a caliber of 0.8 mm to form a primer layer with a thickness of about 25 μm, and the obtained coating (DC) was used as the primer sample of the present application (the same below).

[0065] Fluorosilicon topcoat preparation: the DC sample treated with waterborne zinc-rich epoxy primer was fixed on a spraying sample table, and the coating working solution was uniformly sprayed on the surface of the DC coating layer with a rock gun with a caliber of about 0.8 mm, and the spraying amount was controlled to make the average thickness of the dry topcoat layer about 25.2 μm, and then the coating was leveled at room temperature for 30 min, and then heated to 70°C for 30 min to remove the water in the coating, and then heated to 150°C for 30 min for curing, and the obtained coating was the coating sample prepared based on the waterborne amino epoxy modified fluorosilicon resin EAFSi-1 coating composition.

[0066] Control group 1

[0067] In a three-necked flask equipped with a thermometer, a reflux condenser and a stirrer, 17.65 g of γ-aminopropyltriethoxysilane, 15 g of tridecafluorohexylethyltrimethoxysilane, 32.5 g of dimethyldiethoxysilane and 32.5 g of diphenyldimethoxysilane were added and stirred uniformly. Then 195.3 g of fluorotoluene / ethanol mixed solvent (volume ratio 1:1), 1.95 g of tin diisooctoate catalyst were added, and deionized water in an amount equal to the total amount of alkoxyl group in the system was added dropwise under stirring, and the system was heated to 80°C for hydrolysis and polycondensation reaction for 4 h. After the reaction was completed, the system was heated to about 85°C, and part of the solvent was removed by normal pressure evaporation, and then low boiling point was removed under reduced pressure, and about 64.25 g of transparent viscous liquid was obtained, and the ammonia value was about 1.2409 mmol / g. The fluorotoluene / ethanol mixed solvent was used to dilute the obtained product to a solid content of 30%.

[0068] Take 100 g of the above product, add 0.5 g of wet dispersant, 15.75 g of nano-titanium dioxide / Al(OH)3 powder (mass ratio 1:1), and disperse uniformly with a high-speed disperser. Then add a mixture of fluorotoluene / ethanol solvent to adjust the solid content of the system to about 38.3%, and obtain about 119.45 g of mixture, which is A material.

[0069] Take 52.35 g of E51 epoxy resin, add 0.5 g of wet dispersant, 27.48 g of nano-titanium dioxide / Al(OH)3 powder (mass ratio 1:1), and 25 g of fluorotoluene / ethanol mixture solvent, and disperse uniformly with a high-speed disperser. Then add a mixture of fluorotoluene / ethanol solvent to adjust the solid content of the system to about 38.3%, and obtain about 208.43 g of mixture, which is B material.

[0070] Take 100 g of A material and 55.5 g of B material, adjust with flexible amine curing agent D230 to make the molar ratio of N-H bond in A material+flexible amine curing agent to epoxy group in B material about 1.1:1, mix under stirring, and disperse uniformly with a high-speed disperser. Then remove the gas bubbles under reduced pressure to obtain a solvent-based epoxy resin modified fluorosilicon resin coating.

[0071] The solvent-based epoxy resin modified fluorosilicon resin coating is prepared into a coating layer and evaluated for performance, and it is found that the water contact angle θ H2O is 116.7°, and the adhesion to the metal substrate surface can reach level 1, which is better than that of EAFSi-1 coating. However, for DC samples treated with water-based zinc-rich epoxy primer on the substrate surface, the solvent-based coating is difficult to apply uniformly on the surface of the DC sample due to the influence of hydrophilic and hydrophobic polarity. In addition, the solvent-based coating also shows dissolution and corrosion to the water-based DC coating, which can cause the DC coating to become soft and powder, resulting in partial functional failure of the DC coating. At the same time, the powder formation also leads to a decrease in the overall adhesion of the DC coating-solvent-based coating to level 3, and the powder formation has a certain impact on the performance of the solvent-based coating. The VOC of the solvent-based coating is >60%, and there is high VOC emission pollution during use.

[0072] The solvent type epoxy resin modified fluorosilicon resin coating and the EAFSi-1 coating were respectively sprayed in an 80% atmospheric humidity environment, and then the coating was leveled at room temperature of 25°C for 30 minutes in the 80% humidity environment, the sample was moved into a 70°C oven for drying for 30 minutes, and then the temperature was increased to 120°C for drying for 30 minutes, and the sample was cured at 150°C for 20 minutes to obtain a fluorosilicon resin coating for operation and construction in a high humidity environment. It was found through testing that the moisture adsorbed on the surface of the substrate or the base coating can affect the adhesion of the solvent type fluorosilicon resin coating, the high humidity environment makes the adhesion of the solvent type fluorosilicon resin coating decrease to level 3, and the salt spray resistance of the coating decreases to 700 hours, but the performance of the EAFSi-1 coating is not significantly affected. It is speculated that the high humidity in the environment causes the solvent type coating system to absorb moisture, which causes the epoxy resin modified fluorosilicon resin and the substrate to not form a covalent bond effectively, and a defect is formed. Therefore, the solvent type epoxy resin modified fluorosilicon resin coating is also not suitable for a high humidity environment.

[0073] Example 2

[0074] (1) Preparation of the waterborne amino epoxy modified fluorosilicon resin coating

[0075] Preparation of A2 material: 100.0 g of EAFSi-2 emulsion with a solid content of about 25.0% was taken, and then about 50% of 12.5 g of waterborne nano flame-retardant slurry Al2O3 / Al(OH)3 (mass ratio 1:3) with a solid content of 75% based on the mass of EAFSi-2 resin, 1.0 g of waterborne anti-flash rust agent FA-179, 0.3 g of Tego 810 defoamer, and 2.0 g of waterborne nano silver 930FELX bactericide with an effective content of about 5 wt% were added and uniformly stirred to obtain 115.8 g of a uniform fluid, which was recorded as A2 material, with a solid content of about 30.89% and an N-H content (based on the number of moles of N-H bonds contained in 100 g of A2 material) of about 0.0198 mol / 100 g.

[0076] Preparation of B2 material: 100.0 g of waterborne epoxy resin emulsion with a solid content of about 40% and an epoxy value of about 0.25 was taken, and then about 50% of 20.0 g of waterborne nano flame-retardant slurry Al2O3 / Al(OH)3 (mass ratio 1:3) with a solid content of 75% based on the mass of the solid epoxy resin, 1.0 g of waterborne anti-flash rust agent FA-179, 0.3 g of Tego 810 defoamer, and 2.0 g of waterborne nano silver 930FELX bactericide with an effective content of about 5 wt% were added and uniformly stirred to obtain 123.3 g of a uniform fluid, which was recorded as B2 material, with a solid content of about 30.89% and an epoxy group content (based on the number of moles of epoxy groups contained in 100 g of the coating) of about 0.1369 mol / 100 g.

[0077] (2) Preparation of the waterborne amino epoxy modified fluorosilicon resin coating

[0078] Coating working solution preparation: 100 g of A2 and 100.0 g of B2 were weighed out respectively according to the mass ratio of A2:B2 = 1:1, stirred and mixed uniformly, and then 21.96 g of ARAFUR 3820 modified amine curing agent (Huntsman) with an ammonia value of 170-210, an active hydrogen equivalent of 150, a viscosity of 12000 mPa.s, and a solid content of 80% was used for adjustment to make the molar ratio of N-H bond in the system (A2+adjusting agent) to epoxy group in B2 about 1:1, stirred and mixed uniformly, vacuum degassing, and the coating working solution was obtained.

[0079] Primer treatment: same as Example 1.

[0080] Fluorosilicon surface layer preparation: the DC sample treated with waterborne zinc-rich epoxy primer in Example 1 was fixed on a spraying sample table, and then the coating working solution was uniformly sprayed on the surface of the DC coating layer using a rock gun with a caliber of about 0.8 mm, the spraying amount was controlled to make the thickness of the dry surface coating layer about 26.3 μm, and then the sample was leveled at room temperature for 20 min, and then heated at 70°C for 60 min to remove the water in the coating layer, and then heated to 120°C for curing for 60 min, and the obtained coating layer was the coating sample prepared based on the waterborne amino epoxy modified fluorosilicon resin EAFSi-2 coating composition.

[0081] Example 3

[0082] (1) Preparation of waterborne amino epoxy modified fluorosilicon resin coating

[0083] Preparation of A3: 100.0 g of EAFSi-3 emulsion with a solid content of about 26.50% and an NH content of about 0.0192% was taken, and then about 80% of 21.2 g of waterborne nano flame-retardant slurry CaCO3 / Al(OH)3 (1:1, wt / wt) with a solid content of 72.5% based on the mass of EAFSi-3 resin, 0.75 g of waterborne anti-flash rust agent FA-179, 0.2 g of Tego 810 defoamer from Degussa, and 0.3 g of BIT-1,2-benzisothiazolin-3-ketone bactericide were added, stirred and mixed uniformly, vacuum degassed, and a total of 122.45 g of uniform fluid was obtained, which was recorded as A3 material with a solid content of about 35.21% and an N-H content (calculated based on the number of moles of N-H bond contained in 100 g of A material) of about 0.0157 mol / 100 g.

[0084] B3 material preparation: take 100.0 g of waterborne epoxy resin E44 (Baling Petrochemical Co., Ltd.) with a solid content of about 50% and an epoxy value of about 0.2, then add 80% of the solid epoxy resin, about 40 g of waterborne nano flame retardant slurry Al(OH)3 / CaCO3 (1:1, wt / wt) with a solid content of 72.5%, 0.75 g of waterborne anti-flash rust agent FA-179, 0.2 g of Tego810 defoamer from Degussa, and 0.3 g of BIT-1,2-benzisothiazolin-3-ketone bactericide, mix well, get 141.25 g of uniform fluid, namely B material, dilute with 84.30 g of water to a solid content of about 35.21%, and the epoxy group content is about 0.0878 mol / 100 g of epoxy group contained in 100 g of coating, marked as B3 material.

[0085] (2) Preparation of waterborne amino epoxy modified fluorosilicon resin coating

[0086] Coating working solution preparation: take 100 g of A3 material and 66.67 g of B3 material respectively according to the mass ratio of A3:B3 = 1.5:1, mix well, then adjust with 8.57 g of modified amine adduct curing agent ARAFUR3984 (Huntsman) with an ammonia value of 196-253, active hydrogen equivalent of 150, viscosity of 5500 mPa.s, and solid content of about 80% to make the molar ratio of N-H bond in the system (A3+ adjusting agent) to epoxy group in B3 material about 1.05:1, mix well, and vacuum degassing, then get the coating working solution.

[0087] Primer treatment: same as Example 1.

[0088] Fluorosilicon topcoat preparation: take the DC sample treated with waterborne zinc-rich epoxy primer in Example 1, fix it on the spraying sample table, then use Iwata airbrush with a caliber of about 0.8 mm to uniformly spray the coating working solution on the surface of the DC coating, control the spraying amount to make the thickness of the dry surface coating about 25.8 μm, first level at room temperature for 25 min, then bake at 75 ℃ for 40 min to remove water in the coating, then heat to 130 ℃ and cure for 30 min, the obtained coating is the coating sample prepared based on waterborne amino epoxy modified fluorosilicon resin EAFSi-3 coating composition.

[0089] Control group 2

[0090] Coating working solution preparation: take 100 g of A3 material and 66.67 g of B3 material respectively according to the mass ratio of A3:B3 = 1.5:1, mix well, then adjust with 0.696 g of ethylenediamine to make the molar ratio of N-H bond in the system (A3+ adjusting agent) to epoxy group in B3 material about 1.05:1, mix well, and vacuum degassing, then get the coating working solution EAFSi-3'.

[0091] Primer treatment: same as Example 1.

[0092] Fluorosilicon topcoat preparation: take the DC sample treated with waterborne zinc-rich epoxy primer of Example 1, fix it on the spray sample table, then use the Iyota spray gun with a caliber of about 0.8 mm to uniformly spray the coating working solution on the surface of the DC coating, control the spraying amount so that the thickness of the dry surface coating is about 25.8 μm, first level at room temperature for 25 min, then bake at 75 °C for 40 min to remove water in the coating, then heat to 130 °C and cure for another 30 min, the obtained coating is the coating sample prepared based on the waterborne amino epoxy modified fluorosilicon resin EAFSi-3' coating composition. Test the obtained coating, the salt spray resistance of the coating is less than 700 h, the adhesion is 2 levels, the contact angle θ H2O is 87.3°, and the coating surface has a sticky feeling, and the comprehensive performance is worse than that of the EAFSi-3 coating. Since the modified amine adduct curing agent ARAFUR3984 with high molecular weight is replaced by small molecule ethylenediamine, but ethylenediamine has good solubility in water phase and is easy to volatilize under heat, which makes the reactivity of ethylenediamine in the internal oil phase crosslinking and curing reaction of the coating latex particle poor. During the reaction, a large amount of ethylenediamine volatilizes at 75 °C in the water removal stage, which greatly changes the N-H bond: epoxy group molar ratio in the system from the theoretical value, the N-H bond content is lower than the theoretical value and cannot be controlled, and the change of the ratio further leads to the change of the product structure, and the preset molar ratio curing reaction cannot be completely carried out (i.e. cannot be completely cured), and the coating finally cannot achieve the expected performance.

[0093] Example 4

[0094] (1) Preparation of waterborne amino epoxy modified fluorosilicon resin coating

[0095] Preparation of A4 material: take 100.0 g of EAFSi-4 emulsion with a solid content of about 30.0% and an NH content of about 0.08%, add 75% of the solid content of the waterborne nano flame-retardant slurry ZnO2 / Mg(OH)2 (1:2, wt / wt) based on the mass of the EAFSi-4 resin, about 22.50 g, 0.5 g of waterborne anti-flash rust agent FA-179, 0.2 g of Tego 810 defoamer, 1.0 g of waterborne nano-silver 930FELX bactericide with an effective component content of about 5 wt%, and stir to mix uniformly, to obtain 124.2 g of uniform fluid, which is denoted as A4 material, with a solid content of 37.44% and an N-H content (based on the number of moles of N-H bonds contained in 100 g of A4 material) of about 0.0644 mol / 100 g.

[0096] B4 material preparation: take 100.0 g of waterborne epoxy resin HE44 emulsion with solid content of about 50% and epoxy value of about 0.2, then add about 75% of solid epoxy resin, about 37.5 g of waterborne nano flame retardant slurry ZnO2 / Mg(OH)2(1:2, wt / wt) with solid content of 70%, 0.5 g of waterborne anti-flash rust agent FA-179, 0.2 g of Tego 810 defoamer, 1.0 g of waterborne nano silver 930FELX bactericide with active ingredient content of about 5 wt%, stir and mix evenly to obtain 139.2 g of uniform fluid, i.e. B material, dilute with water to a solid content of about 37.44%, and the epoxy group content is about 0.0972 mol / 100 g of epoxy groups contained in 100 g of coating, denoted as B4 material.

[0097] (2) Preparation of waterborne amino epoxy modified fluorosilicon resin coating

[0098] According to the mass ratio of A4:B4=1:1, 100 g of A4 material and 100.0 g of B4 material are stirred and mixed, and then 7.11 g of end group type DETA-E44-DETA modified amine water emulsion prepared by reacting diethylenetriamine DETA with epoxy resin E44 with viscosity of about 5000 mPa.s, active hydrogen equivalent of 83.61 and solid content of about 50% is added to adjust the molar ratio of N-H bond in the system (A4+adjusting agent) to epoxy group in B4 material to about 1.1:1, and then stirred and mixed, and vacuum degassed to obtain a coating working solution.

[0099] Primer treatment: same as Example 1.

[0100] Fluorosilicon topcoat preparation: take the DC sample treated with waterborne zinc-rich epoxy primer in Example 1, fix it on a spraying sample table, then use a rockda spraying gun with a caliber of about 0.8 mm to uniformly spray the coating working solution on the surface of the DC coating, control the spraying amount so that the thickness of the dry surface coating is about 27.3 μm, first level at room temperature for 30 min, then bake at 70°C for 45 min to remove water in the coating, then heat to 120°C and cure for 40 min, and the obtained coating is the coating sample prepared based on the waterborne amino epoxy modified fluorosilicon resin EAFSi-4 coating composition.

[0101] Example 5

[0102] Take the EAFSi-1~4 coating samples prepared in Examples 1-4, and balance for 24 h at room temperature (25±2°C) and relative humidity RH of about 58%, and then perform the following coating performance tests:

[0103] Coating surface water repellency: the static contact angle (θ H2O) represents, measured by JC-2000C1 type static contact angle measuring instrument, water droplet size is about 5 μL; salt spray resistance: 5wt% NaCl aqueous solution is used as test liquid, reference GB / T 10125-1997 standard, YWX / Q-150 salt spray resistance tester is used for measurement; hardness: reference GB / T6739-1996 method, pencil hardness is used for evaluation; impact resistance: reference GB / T1732-1993 standard, impact resistance tester is used for measurement; adhesion: reference HGT3792-2014 standard, electric adhesion tester is used for measurement; coating antifouling performance: fly ash method specified in GB / T 9780-1988 is used for measurement, divided into 0, 1, 2, 3, 4 five grades, 0 grade is the best; coating flame retardant performance: vertical burning method is used for evaluation, that is, coating sample is taken, vertically suspended in the combustion test box, ignited by the specified fire source for 12s, after removing the fire source, the afterburning time of the coating sample is measured by a stopwatch. The performance test results of the coating composition and coating sample prepared in examples 1-4 are shown in table 3.

[0104] Table 3 Performance test results of the coating prepared based on the modified fluorosilicon resin water-based emulsion

[0105]

[0106]

[0107] From table 3, it can be seen that the coating sample prepared in examples 1-4 of the present application has a water contact angle θ H2O on the coating surface of 101.3-115.6, the salt spray resistance of the coating reaches 1000h one-way corrosion ≤2mm (good salt spray resistance), the water resistance reaches 168h without bubbling and falling off, the hardness reaches 1H-3H, the impact resistance reaches 50-70cm, the antifouling grade generally reaches 0-1, and the vertical burning time of the coating is only 1.13-2.57s, which shows that the fluorosilicon coating prepared based on the water-based EAFSi resin of the present application not only has good adhesion and impact resistance, but also is flame-retardant, waterproof, antifouling, salt spray resistant and low in VOC emission, and the coating as a whole shows good comprehensive application effect.

Claims

1. An aqueous modified fluoro-silicone resin coating composition comprising Part A and Part B, characterized in that, The A material comprises 100 parts of amino-epoxy modified fluorosilicone resin EAFSi emulsion with solid content of 25-30%, 0.5-1 part of anti-tarnish agent, 0.1-0.3 part of defoaming agent, 0.1-2.0 part of bactericide, and 50-80% of aqueous nano flame-retardant slurry with solid content of 70-75% based on the mass of the amino-epoxy modified fluorosilicone resin EAFSi; The B material comprises 100 parts of second aqueous epoxy resin ER-B emulsion with solid content of 40-60%, 0.5-1 part of anti-tarnish agent, 0.1-0.3 part of defoaming agent, 0.1-2.0 part of bactericide, and 50-80% of aqueous nano flame-retardant slurry with solid content of 70-75% based on the mass of the second aqueous epoxy resin ER-B; The amino-epoxy modified fluorosilicone resin EAFSi is a fluorosilicone copolymer containing D-type and / or T-type siloxane segments and amino-silane modified epoxy resin segments; the amino-epoxy modified fluorosilicone resin EAFSi emulsion has solid content of 25-30% and N-H bond content of 0.01-0.1 mol / 100g based on the moles of N-H bonds contained in 100g of the amino-epoxy modified fluorosilicone resin EAFSi emulsion; The second aqueous epoxy resin ER-B is a bisphenol A epoxy resin or a hydrogenated bisphenol A epoxy resin; The composition further comprises a modified amine curing agent which is an amine curing agent formed by ring-opening modification of an epoxy resin with an organic polyamine.

2. The composition of claim 1, wherein, The amino epoxy-modified fluorosilicone resin EAFSi is EASi-co-aminoalkylsiloxane-co-fluoroalkylsiloxane-co-C 1-18 alkylsiloxane-co-phenylsiloxane, EASi-co-aminoalkylsiloxane-co-fluoroalkylsiloxane-co-C 1-18 alkylsiloxane or EASi-co-aminoalkylsiloxane-co-fluoroalkylsiloxane-co-phenylsiloxane; The EASi is an amino-silane ring-opening modified epoxy resin segment; The amino-hydroxy group is a γ-aminopropyl group, an N-cyclohexyl-γ-aminopropyl group, an N-β-aminopropyl-γ-aminopropyl group, an N,N-dimethyl-γ-aminopropyl-γ-aminopropyl group, or a piperazinylpropyl group; said fluorocarbon group is C 1-8 one or more of perfluoroalkyl ethyl, perfluoroaryl, perfluoropolyether The C 1-18 Alkyl is one or more of n-alkyl, isoalkyl, or cycloalkyl groups having 1 to 18 carbon atoms in the structure.

3. The composition of claim 2, wherein, EASi-co-aminoalkylsiloxane-co-fluoroalkylsiloxane-co-C 2-18 alkylmethylsiloxane-co-phenylsiloxane, EASi-co-aminoalkylsiloxane-co- fluoroalkylsiloxane-co-C 2-18 alkylmethylsiloxane-co-phenylsiloxane, EASi-co-aminoalkylsiloxane-co- fluoroalkylsiloxane-co-C 2-18 alkylmethylsiloxane-co-phenylsiloxane, EASi-co-aminoalkylsiloxane-co- fluoroalkylsiloxane-co-C 2-18 alkylmethylsiloxane-co-phenylsiloxane, EASi-co-aminoalkylsiloxane-co- fluoroalkylsiloxane-co-C 2-18 alkylmethylsiloxane-co-phenylsiloxane, EASi-co-aminoalkylsiloxane-co- fluoroalkylsiloxane-co-C 2-18 alkylmethylsiloxane-co-phenylsiloxane, EASi-co-aminoalkylsiloxane-co- fluoroalkylsiloxane-co-C alkylmethylsiloxane-co-phenylsiloxane, EASi-co-aminoalkylsiloxane-co- fluoroalkylsiloxane-co-C 4. The composition of claim 1, wherein, The amino-epoxy modified fluorosilicone resin EAFSi emulsion is obtained by a method comprising the following steps: 1) Synthesis of amino-silane ring-opening modified epoxy resin EASi The first epoxy resin ER-A and the first amino-silane ASi-1 are weighed according to a molar ratio of epoxy groups in the first epoxy resin ER-A to the first amino-silane ASi-1 of 1:1-1.1; the first amino-silane ASi-1 is stirred and mixed uniformly with alkyl silane RSi and / or phenyl silane PSi, then heated to 40-60°C, and the first epoxy resin ER-A is added dropwise for aminolysis ring-opening reaction for 30-60 min to obtain a solution of the amino-silane ring-opening modified epoxy resin EASi dispersed in the alkyl silane RSi and / or phenyl silane PSi medium; the mass of the alkyl silane RSi and / or phenyl silane PSi is 100-150% of the total mass of the first epoxy resin ER-A and the first amino-silane ASi-1; 2) Preparation of amino-epoxy modified fluorosilicone resin EAFSi aqueous emulsion to the amino silane open ring modified epoxy resin EASi solution obtained in step 1), adding alkyl silane RSi and / or phenyl silane PSi, fluoroalkyl silane R f Si, and a second amino silane ASi-2, so that the mass ratio of EASi: RSi and / or PSi: R f Si: ASi-2 is 5-10: 40-75: 10-30: 10-20, stirring and mixing to obtain a mixture M; the first amino silane ASi-1 and the second amino silane ASi-2 are the same or different; According to the mass of the mixture M, 5-10% of the anionic surfactant and / or the non-ionic surfactant based on the mass of the mixture M is weighed, water is added for dissolution, the pH is adjusted to 9-10, and the mixture M is added by stirring and heating to 60-80℃, the dropping speed is controlled to be dropped in 1-2h, and then the reaction is kept for 6-10h to obtain the amino epoxy modified fluorosilicon resin EAFSi emulsion.

5. The composition of claim 4, wherein, The first epoxy resin ER-A is one of bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, glycidyl ether epoxy resin, glycidyl ester epoxy resin, linear aliphatic epoxy resin or alicyclic epoxy resin; the first epoxy resin ER-A is the same as or different from the second water-based epoxy resin ER-B; The alkylsilane RS1is a silane containing 1-2 C 1-18 alkyl and 2-3 alkoxy groups; The phenyl silane PSi is a silane containing 1-2 phenyl groups and 2-3 alkoxy groups in the structure; The first amino silane ASi-1 and the second amino silane ASi-2 are silanes containing primary amino groups or / and secondary amino groups and 2-3 alkoxy groups; said fluorohydrocarbylsilane R f Si, containing 1 C 1-8 silanes containing a perfluoroalkylethyl, a perfluoroaryl or / and a perfluoropolyether group and 2-3 alkoxy groups; The alkoxy group is a methoxy group or an ethoxy group.

6. The composition of claim 4, wherein, The first epoxy resin ER-A is one of bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, glycidyl ether epoxy resin, glycidyl ester epoxy resin, linear aliphatic epoxy resin or alicyclic epoxy resin; The first amino silane ASi-1 and the second amino silane ASi-2 are one of aminoalkyl trialkoxysilane and aminoalkyl methyl dialkoxysilane; said fluorocarbon-based silane R f Si is one or two to three of a C1-8 perfluoroalkylethyl trialkoxysilane, a C1-8 perfluoroalkylethyl methyl dialkoxysilane, a 3-heptafluoroisopropoxypropyl trialkoxysilane, a 3-heptafluoroisopropoxypropyl methyl dialkoxysilane, a pentafluorophenyl trialkoxysilane, a pentafluorophenyl methyl dialkoxysilane, a perfluoro polyether-based trialkoxysilane, or a perfluoro polyether-based methyl dialkoxysilane; The alkylsilane RSi is C 1-18 alkyltrialkoxysilane, C 1-18 alkylmethyldialkoxysilane, C 5-6 cycloalkyltrialkoxysilane, C 5-6 one or more of cycloalkylmethyldialkoxysilane, diethyldialkoxysilane; The phenyl silane PSi is one or more of phenyl trialkoxysilane, methyl phenyl dialkoxysilane and diphenyl dialkoxysilane; The non-ionic surfactant is one of fluorocarbon alkyl polyoxyethylene ether, fatty alcohol polyoxyethylene ether, alkyl phenol polyoxyethylene ether, fatty acid polyoxyethylene ether ester and fatty acid sorbitan polyoxyethylene ether ester; The anionic surfactant is one of isomeric fatty alcohol polyoxyethylene ether sodium sulfate, perfluorinated nonyloxy benzene sulfonic acid sodium, perfluorinated polyether carboxylic acid sodium, fatty alcohol polyoxyethylene ether carboxylate, secondary alkyl sulfonate sodium, sodium dodecyl sulfate or potassium dodecyl sulfate.

7. The composition of claim 1, wherein, The second water-based epoxy resin ER-B emulsion is obtained by emulsifying the second water-based epoxy resin ER-B in water under the action of a non-ionic epoxy polyether polymer surfactant, the solid content is 40-60%, and the epoxy group content is 0.2-0.25 mol / 100g in terms of the number of moles of epoxy groups contained in 100g of the emulsion.

8. The composition of claim 1, wherein, The water-based nano flame-retardant slurry is a dispersion of inorganic nano-powder containing a flame retardant in water under the action of a coating additive; the average particle size of the water-based nano flame-retardant slurry is ≤25μm, and the solid content is 70-75%; the inorganic nano-powder is a composite of inorganic nano-TiO2, zinc oxide, calcium carbonate, ferroferric oxide or di-aluminum oxide and a flame retardant aluminum hydroxide or magnesium hydroxide in a mass ratio of 1:1-3; The anti-flash rust agent is FA179 of Hemen or R-765 of Tianjin Qikai Chemical Industry; The defoaming agent is Tego 810 defoaming agent produced by Degussa Company. The bactericide is an isothiazolone bactericide or water-soluble nano-silver widely used in water-based coating systems.

9. A method of producing a waterborne modified fluoro-silicone resin coating from the waterborne modified fluoro-silicone resin coating composition according to any one of claims 1 to 8, characterized in that, The A material and the B material in the composition are mixed in a mass ratio of A material:B material=1-2:1, and then a modified amine curing agent is used for adjustment, so that the molar ratio of total N-H bonds to total epoxy groups in the system is 1-1.1:1, to obtain a coating working solution; The water-based epoxy zinc-rich primer is used as a bottom coating DC sample; the coating working solution is sprayed on the surface of the DC, and then leveled, dried at 70-80°C to remove water, and cured at 120-150°C, to obtain a coating prepared based on a water-based modified fluorosilicon resin coating; The modified amine curing agent is an emulsion of an end group PA-ER-PA product obtained by ring-opening modification of an epoxy resin ER and an organic polyamine PA, which is emulsified in water, and the solid content is 50-80%.

10. An aqueous modified fluorosilicon resin coating obtained by the method of claim 9.

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