阅读说明：本技术 一种双组份超疏水涂料 (Double-component super-hydrophobic coating ) 是由 姬振行 王少华 张海凤 王宇川 于 2020-03-31 设计创作，主要内容包括：本发明提供了一种双组份超疏水涂料,包括底漆和面漆,所述底漆包括如下重量份的原料：100-150份丙烯酸酯树脂,20-35份海因环氧树脂,110-150份无机疏水填料,80-150份稀释剂,2-5份固化剂；所述面漆包括如下重量份的原料：2-5份硅酸酯,7-12份含氟硅烷,15-20份含氟丙烯酸基树脂,2-5份无机疏水填料,0.5-1份有机锡催化剂,60-80份面漆溶剂；所述含氟丙烯酸基树脂中的聚合单体包括式(I)结构所示的丙烯酸-(氟代烷氧基苯基)烷基酯。所述双组份超疏水涂料具有有益的超疏水性能,而且在高温高湿高盐度的环境下能够长时间保持优异的超疏水性能,特别适用于电气柜的防水防潮防凝露的涂料。(The invention provides a two-component super-hydrophobic coating which comprises a primer and a finish, wherein the primer comprises the following raw materials in parts by weight: 100-150 parts of acrylate resin, 20-35 parts of hydantoin epoxy resin, 110-150 parts of inorganic hydrophobic filler, 80-150 parts of diluent and 2-5 parts of curing agent; the finish paint comprises the following raw materials in parts by weight: 2-5 parts of silicate ester, 7-12 parts of fluorine-containing silane, 15-20 parts of fluorine-containing acrylic resin, 2-5 parts of inorganic hydrophobic filler, 0.5-1 part of organic tin catalyst and 60-80 parts of finish solvent; the polymerized monomer in the fluorine-containing acrylic acid-based resin comprises acrylic acid- (fluoroalkoxyphenyl) alkyl ester shown in a structure of formula (I). The two-component super-hydrophobic coating has beneficial super-hydrophobic performance, can maintain excellent super-hydrophobic performance for a long time in high-temperature, high-humidity and high-salinity environments, and is particularly suitable for waterproof, moistureproof and anti-condensation coatings of electrical cabinets.)

1. The two-component super-hydrophobic coating comprises a primer and a finish, wherein the primer comprises the following raw materials in parts by weight: 100-150 parts of acrylate resin, 20-35 parts of hydantoin epoxy resin, 110-150 parts of inorganic hydrophobic filler, 80-150 parts of diluent and 2-5 parts of curing agent; the finish paint comprises the following raw materials in parts by weight: 2-5 parts of silicate ester, 7-12 parts of fluorine-containing silane, 15-20 parts of fluorine-containing acrylic resin, 2-5 parts of inorganic hydrophobic filler, 0.5-1 part of organic tin catalyst and 60-80 parts of finish solvent; the polymerized monomer in the fluorine-containing acrylic acid-based resin comprises acrylic acid- (fluoroalkoxyphenyl) alkyl ester shown in a structure of a formula (I):

wherein n is an integer from 1 to 3, such as 1, 2, 3; m is an integer from 3 to 6, such as 3, 4, 5, 6.

2. The superhydrophobic coating of claim 1, wherein the fluorine-containing acrylic-based resin is an alkyl (meth) acrylate, a- (fluoroalkoxyphenyl) alkyl acrylate, and 5-10 parts of an itaconic-based epoxy resin at a mass feed ratio of 20-30: 10-15: 1-1.5.

3. The superhydrophobic coating of claim 2, wherein the alkyl ester of the alkyl (meth) acrylate is an ester having 1-8 carbon atoms, preferably methyl acrylate, methyl methacrylate, butyl acrylate, ethyl methacrylate, ethyl acrylate, or isooctyl methacrylate, preferably isooctyl methacrylate.

4. The superhydrophobic coating of claim 2, wherein the fluorine-containing acrylic acid-based resin is obtained by a preparation method comprising:

mixing monomers of alkyl (meth) acrylate, acrylic acid- (fluoroalkoxyphenyl) alkyl ester and itaconic acid-based epoxy resin in a mass ratio of 20-30: 10-15: 1-1.5, adding into an organic solvent, adding an initiator, stirring and reacting for 15-20 hours at 60-80 ℃ under the condition of nitrogen, precipitating the reaction solution by using a precipitator after the reaction is finished, filtering, drying and grinding in vacuum to obtain the fluorine-containing acrylic acid based resin.

5. The superhydrophobic coating of claim 1, wherein the acrylate resin is a polymer of an alkyl (meth) acrylate selected from the group consisting of ethyl acrylate, ethyl methacrylate, propyl acrylate, isopropyl methacrylate, butyl acrylate, butyl methacrylate, pentyl acrylate, pentyl methacrylate, hexyl acrylate, hexyl methacrylate.

6. The superhydrophobic coating of claim 1, wherein the inorganic hydrophobic filler is at least one of hydrophobically modified heavy calcium carbonate powder, modified white carbon black, hydrophobic diatomaceous earth, and hydrophobic wollastonite powder, wherein the hydrophobically modified heavy calcium carbonate powder is stearic acid modified heavy calcium carbonate powder, and the modified white carbon black is fumed silica modified with a silane coupling agent selected from at least one of KH-540, KH-550, KH-560, KH-570, KH-792, Si-602, and Si-563.

7. The superhydrophobic coating of claim 1, wherein the silicate is an orthosilicate or a polysilicate, the orthosilicate selected from at least one of tetramethyl orthosilicate, tetraethyl orthosilicate, tetraiso orthosilicate, tetrabutyl orthosilicate; the polysilicate is an oligomer obtained by hydrolyzing and condensing orthosilicate; and/or

The fluorine-containing silane is (3, 3, 3-trifluoropropyl) trimethoxysilane, (3, 3, 3-trifluoropropyl) trichlorosilane, (3, 3, 3-trifluoropropyl) triethoxysilane, 1H, 1H, 2H, 2H-perfluorodecyl triethoxysilane or trichloro- (1H, 1H, 2H, 2H-perfluorooctyl) silane, trimethoxy- (1H, 1H, 2H, 2H-perfluorooctyl) silane, triethoxy- (1H, 1H, 2H, 2H-perfluorooctyl) silane.

8. The super-hydrophobic coating as claimed in claim 1, wherein the inorganic hydrophobic filler in the finish paint component is a compound of hydrophobic heavy calcium powder and modified white carbon black according to a mass ratio of 1-2: 4-6.

9. A method of applying the two-component superhydrophobic coating of any of claims 1-8 by first applying a primer to the surface to be treated, and then applying a topcoat after the primer has dried; the thickness of the primer is 10-20 μm, and the thickness of the finish paint is 5-10 μm.

10. Use of the two-component superhydrophobic coating according to any of claims 1-8 for superhydrophobic, self-cleaning surface treatment of substrate materials, glass, wall surfaces, metal, fabrics, especially for surfaces of electrical cabinets.

Technical Field

The invention relates to the technical field of hydrophobic materials, in particular to a two-component super-hydrophobic coating.

Background

The super-hydrophobic material is a material with a contact angle with a water drop larger than 150 degrees and a rolling angle smaller than 10 degrees, and has very wide application prospect in the daily life field and the industrial field because the super-hydrophobic property of the super-hydrophobic material shows a plurality of unique and beneficial properties, such as self-cleaning property, anticorrosion and antifouling property, antifogging property, waterproof property and self-cleaning property. For example, the glass fiber reinforced plastic has great application potential in the fields of fabrics, buildings, electric appliances, glass products, antennas and the like.

The super-hydrophobic material is widely concerned in the industry, and various materials and preparation methods are reported, but three key problems exist for the final industrial application. Firstly, the production scale-up is limited by the preparation process of the micro-nano material with a complex product; secondly, the binding property and certain durability of the constructed surface and the base material; thirdly, the high preparation cost limits the practical application. The introduction of superhydrophobic materials into the field of daily life is a great problem.

With the development of modern electrification technology, the integration and intensification of electrical appliances become the mainstream development trend. The electric integrated control or operation cabinet is widely applied to the fields of chemical industry, environmental protection, electric power, metallurgy, nuclear industry, fire safety monitoring, traffic and the like. The regulator cubicle and inside components and parts are made by the metal mostly, because the service environment of different trades regulator cubicles is different, and the climatic conditions of each place is also different, and the inside and the outside of regulator cubicle all receive the erosion of moisture easily, and then cause the corrosion, seriously influence the life of regulator cubicle and inside components and parts, and then influence whole electrical system's use. Especially, the distribution network electrical cabinet is generally exposed outdoors and is easily influenced by external climatic environment, for example, weather with large temperature difference change, humid weather, marine climate and the like easily cause condensation in the distribution network electrical cabinet, and serious consequences such as failure or burnout of electrical components, tripping of switch equipment and the like are easily caused. At present, heating and ventilation dehumidification are mainly used for solving the problems, but the effect is not remarkable.

At present, organosilicon coatings are mostly adopted, vinyl organosilicon is mostly adopted as resin, hydrogen-containing silicone oil is adopted as a cross-linking agent, and the obtained coatings have dry and hard handfeel and large friction force due to higher curing temperature. Patent CN105131833A discloses that paraffin wax is added into silicone composition, and paraffin wax molecules penetrate out of the surface of the coating to reduce the surface adhesion and improve the strippability of the silicone coating. However, after the paraffin is added, the flame retardance of the material is poor, and the safety of the anti-condensation material for electrical equipment is not met. Moreover, the material is easy to be oxidized and deteriorated, the color becomes dark, and even the material gives off odor.

The method is a feasible method for coating the casing of the electrical cabinet with the super-hydrophobic coating, so that the service life of the electrical cabinet can be effectively prolonged, and the safety and stability of the operation of the electrical cabinet are improved. In general, a fluorinated alkyl compound or a fluorine-containing silicon material is used for a super-hydrophobic coating material, and a perfluorinated carbon chain has excellent stability and hydrophobic property, and is widely applied to various hydrophobic materials, wherein a perfluorocarbon chain having a carbon number of 8 or more in a fluorocarbon chain is more studied to provide, and a rigid perfluoroalkyl group can be crystallized or forms a stable liquid crystal structure arrangement, -CF₂The groups can be tightly packed on the surface of the outer layer, and stable and low surface free energy is obtained. Therefore, it is currently doneThe carbon number of the fluorine-containing carbon chain for hydrophobic modification is generally more than or equal to 8. However, these long-chain perfluorocarbon chains are one of the most difficult organic pollutants known at present to degrade, and cause serious environmental pressure during processing and use, and may cause pollution. After the super-hydrophobic coating is coated on an outdoor electric cabinet, the super-hydrophobic performance is gradually reduced in a daily wind-blowing and sun-drying environment, and the coating needs to be re-coated for a period of time, so that the labor cost and the coating cost are increased. In addition, generally, the super-hydrophobic coating is added with the hydrophobic modified fumed silica inorganic hydrophobic filler, so that the problem of powder falling is often caused, namely the wear resistance of the coating is also to be improved.

Patent CN110615998 discloses a wear-resistant super-hydrophobic coating composition which is a three-component coating composition, wherein component A is super-hydrophobic diatomite dispersion liquid with active groups, so that the affinity of paper winding resin is enhanced, and the integral compactness of a coating is improved. The obtained hydrophobic material has good wear resistance, and still keeps excellent super-hydrophobic performance after being rubbed by abrasive paper for many times. However, the coating is applied to the electrical cabinet, particularly the surface of a field electrical cabinet is waterproof, the anti-condensation coating is used, and the super-hydrophobic performance is reduced rapidly after long-time use in the air atmosphere with high humidity and high salinity. The actual requirements of the coating for the electrical cabinet cannot be met. Patent CN110606989A discloses a super-hydrophobic graphene wind power blade surface protective coating material, which has weather resistance, wear resistance, excellent adhesive force and corrosion resistance. However, the graphene-based material with high price is used, the cost is high, the cost is unacceptable for the coating which needs to be applied to the electrical cabinet in a large area, and the coating cannot be used as an industrialized super-hydrophobic coating for the electrical cabinet. Patent CN105238246A discloses an environment-friendly super-hydrophobic composite material and a preparation method thereof, and specifically, a silane coupling agent is adopted for agglomeration to form a micro-nano structure, then a hydrophobic agent is used for hydrophobic modification, and the hydrophobic modification is blended with polyurethane-acrylate to prepare the super-hydrophobic composite material. The hydrophobic agent is long-chain alkyl silane. The polyurethane-acrylate emulsion is used as a film forming agent, so that the adhesive force of the super-hydrophobic composite material is improved, and the powder falling phenomenon is improved. But the superhydrophobic property of the material can not meet the requirements of waterproof and anti-condensation coatings of the electrical cabinet. CN103436138A discloses a stable transparent super-hydrophobic material, which can be constructed into a transparent super-hydrophobic or super-amphiphobic coating with excellent super-hydrophobic performance. However, long-term hydrophobic performance of the electrical cabinet needs to be tested, especially in southern coastal areas, the high-temperature, high-humidity and high-salinity air can cause the corrosion of salt fog on components in the electrical cabinet, so that the service life of the electrical cabinet is shortened, and the dangerous hidden danger is increased. Salt fog climate in coastal areas has a more serious corrosion and destruction effect on electronic products, and the closer to the sea, the more serious the corrosion phenomenon on the electrical cabinet. Besides corrosion to electrical equipment, after salt mist is absorbed by some insulators, the surface resistance is greatly reduced, the use of a circuit board is seriously influenced, and the risk of short circuit is greatly improved.

Disclosure of Invention

In order to solve the problem of insufficient hydrophobicity of the coating in the prior art, the invention provides the two-component super-hydrophobic coating with excellent comprehensive performance, which still keeps excellent hydrophobic and self-cleaning effects after long-term use and has good wear resistance. The super-hydrophobic coating disclosed by the invention is simple in coating process and divided into two components of the primer and the finish, when the super-hydrophobic coating is coated, the primer is coated firstly, and then the finish is coated on the primer, so that excellent hydrophobic, anti-condensation and self-cleaning effects can be achieved, and meanwhile, the defect that the hydrophobicity of a common hydrophobic material is reduced in air with high heat, high humidity and high salinity is overcome.

The invention aims to provide a two-component super-hydrophobic coating which comprises a primer and a finish, wherein the primer comprises the following raw materials in parts by weight: 100-150 parts of acrylate resin, 20-35 parts of hydantoin epoxy resin, 110-150 parts of inorganic hydrophobic filler, 80-150 parts of diluent and 2-5 parts of curing agent; the finish paint comprises the following raw materials in parts by weight: 2-5 parts of silicate ester, 7-12 parts of fluorine-containing silane, 15-20 parts of fluorine-containing acrylic resin, 2-5 parts of inorganic hydrophobic filler, 0.5-1 part of organic tin catalyst and 60-80 parts of finish solvent; the polymerized monomer in the fluorine-containing acrylic acid-based resin comprises acrylic acid- (fluoroalkoxyphenyl) alkyl ester shown in a structure of a formula (I):

wherein n is an integer from 1 to 3, such as 1, 2, 3; m is an integer from 3 to 6, such as 3, 4, 5, 6.

The fluorine-containing acrylic resin is prepared from (methyl) acrylic acid alkyl ester, acrylic acid- (fluoroalkoxyphenyl) alkyl ester and 5-10 parts of itaconic acid-based epoxy resin according to a mass ratio of 20-30: 10-15: 1-1.5.

Wherein the alkyl ester in the alkyl (meth) acrylate is an ester having 1 to 8 carbon atoms, and specific examples of the alkyl (meth) acrylate include, but are not limited to, methyl acrylate, methyl methacrylate, butyl acrylate, ethyl methacrylate, ethyl acrylate, or isooctyl methacrylate, and isooctyl methacrylate is preferable.

The fluorine-containing acrylic acid-based resin is obtained by a preparation method comprising the following steps:

mixing monomers of alkyl (meth) acrylate, acrylic acid- (fluoroalkoxyphenyl) alkyl ester and itaconic acid-based epoxy resin in a mass ratio of 20-30: 10-15: 1-1.5, adding into an organic solvent, adding an initiator, stirring and reacting for 15-20 hours at 60-80 ℃ under the condition of nitrogen, precipitating the reaction solution by using a precipitator after the reaction is finished, filtering, drying and grinding in vacuum to obtain the fluorine-containing acrylic acid based resin.

Wherein the using amount of the initiator is 0.5-2% of the total mass of the monomers; the volume consumption of the organic solvent is 2-5 times (ml/g) of the total mass of the monomers.

In the above polymerization method, the organic solvent, the initiator and the precipitant are not particularly limited, and a conventional solvent and an initiator for polymerization of an acrylic monomer are generally used. In the practice of the present invention, the organic solvent used includes, but is not limited to, at least one of toluene, xylene, tetrahydrofuran, cyclohexanone, methyl isobutyl ketone, ethyl acetate; the initiator includes, but is not limited to, at least one of azobisisobutyronitrile, diisobenzoyl peroxide, potassium persulfate, and sodium persulfate. The precipitator is a mixed solution of water and low-carbon alcohol according to the mass ratio of 1-2: 4-6.

The invention utilizes the acrylate containing the long-chain perfluoroalkyl group with the phenylate structure shown in the formula (I) to replace the fluoroalkyl acrylate frequently used in the general super-hydrophobic material, thereby ensuring the degradability and environmental protection of the material and simultaneously meeting the super-hydrophobic characteristic of the material. And the inventor creatively discovers that the fluorine-containing acrylic acid-based resin obtained by copolymerizing acrylic acid- (fluoroalkoxyphenyl) alkyl ester serving as a fluorine-containing monomer and alkyl acrylate has excellent super-hydrophobic performance, maintains stable and good compatibility and bonding force with a primer, and ensures excellent performance of long-term use as a hydrophobic surface treatment material. The inventor unexpectedly discovers that itaconic acid-based epoxy resin is introduced into a monomer of the fluorine-containing resin in a certain proportion, the hydantoin epoxy resin is provided with carbon-carbon double bonds which can participate in free radical polymerization, and ester bonds in the hydantoin epoxy resin can be degraded under certain conditions, so that the problem of environmental pollution caused by difficult degradation of the fluorine-containing resin is further avoided; after the itaconic acid-based epoxy resin is added, the hydrophobicity of the material is not adversely affected, the defect that the superhydrophobicity of the superhydrophobic material is reduced quickly under the air atmosphere with high temperature, high humidity and high salinity for a long time is greatly overcome, the superhydrophobic coating disclosed by the invention is ensured to be waterproof in an electric cabinet, and when the anti-condensation coating is used, the electrical components in the electric cabinet are prevented from being corroded by water vapor, particularly in the coastal areas in the south, the advantages can be fully exerted due to the fact that the air humidity is high and the salinity is high, and the excellent waterproof and anti-condensation effects can be still ensured after long-time use.

In a preferred embodiment of the present invention, in the components of the primer:

the acrylate resin is a polymer of alkyl (meth) acrylate such as ethyl acrylate, ethyl methacrylate, propyl acrylate, isopropyl methacrylate, butyl acrylate, butyl methacrylate, pentyl acrylate, pentyl methacrylate, hexyl acrylate, hexyl methacrylate, cyclohexyl methacrylate, and preferably is butyl methacrylate resin.

The inorganic hydrophobic filler is at least one of hydrophobic modified coarse whiting powder, modified white carbon black, hydrophobic diatomite and hydrophobic wollastonite powder, wherein the hydrophobic modified coarse whiting powder is stearic acid modified coarse whiting powder, the modified white carbon black is silane coupling agent modified fumed silica, and the silane coupling agent is at least one of KH-540, KH-550, KH-560, KH-570, KH-792, Si-602 and Si-563.

The diluent is selected from at least one of ethyl acetate, propyl acetate, butyl acetate, toluene, xylene and tetrahydrofuran;

preferably, the primer component further comprises the following auxiliary materials in parts by weight: 3-6 parts of oily dispersing agent, 3-6 parts of oily defoaming agent and 1-3 parts of flatting agent.

The oily dispersant is at least one selected from BYK-P104S and Merck MOK 5623.

The oily antifoaming agent is polysiloxane antifoaming agent, such as at least one of Wake SD986, Michelia TSA-750S;

the leveling agent is polyether modified polysiloxane, such as at least one of EH-3411, NBNK-L K306, KV-503 and KV-506.

In an embodiment of the present invention, in the components of the top coat:

the silicate is orthosilicate or polysilicate, and the orthosilicate is at least one selected from tetramethyl orthosilicate, tetraethyl orthosilicate, tetraiso-orthosilicate and tetrabutyl orthosilicate; the polysilicate refers to an oligomer obtained by condensation after hydrolysis of orthosilicate.

The fluorine-containing silane is (3, 3, 3-trifluoropropyl) trimethoxysilane, (3, 3, 3-trifluoropropyl) trichlorosilane, (3, 3, 3-trifluoropropyl) triethoxysilane, 1H, 1H, 2H, 2H-perfluorodecyl triethoxysilane or trichloro- (1H, 1H, 2H, 2H-perfluorooctyl) silane, trimethoxy- (1H, 1H, 2H, 2H-perfluorooctyl) silane, triethoxy- (1H, 1H, 2H, 2H-perfluorooctyl) silane.

The inorganic hydrophobic filler of the finish paint component is preferably a compound of hydrophobic heavy calcium powder and modified white carbon black according to the mass ratio of 1-2: 4-6. The inventor finds that the hydrophobic performance of the material can be further improved by adopting the hydrophobic heavy calcium powder and the modified white carbon black which are compounded in a certain proportion.

The catalyst is at least one of organic tin catalyst and platinum catalyst. The organic tin is dibutyl tin diacetate, diethyl tin dilaurate or dibutyl tin dilaurate.

The finishing paint solvent is at least one of alcohol, DMF and THF.

The second purpose of the invention is to provide an application method of the two-component super-hydrophobic coating, which is to apply a primer on the surface to be treated, and apply a finish after the primer is dried.

The drying is natural drying or drying. The manner of application is not particularly limited and is well known in the art as one of dip coating, spray coating, spin coating, roll coating and brush coating, and in one embodiment of the present invention is spray coating to more uniformly cover the surface of the material to be treated.

The thickness of the primer is 20-30 μm, and the thickness of the finish paint is 10-20 μm.

The third purpose of the invention is to provide the application of the two-component super-hydrophobic coating, in particular to super-hydrophobic and self-cleaning surface treatment of a substrate material, wherein the substrate material is glass, wall surface, metal or fabric (such as umbrella), and is particularly suitable for the surface of an electrical cabinet.

The invention has the advantages of

Compared with the super-hydrophobic coating provided in the prior art, the two-component super-hydrophobic coating provided by the invention is prepared by firstly coating a primer on the surface to be treated, and then coating a finish after drying. The surface of the treated fabric has excellent hydrophobic property, and the contact angle of the treated fabric with water is more than 150 degrees.

The inventors have unexpectedly found that the fluorine-containing acrylic acid derivative of formula (I) is copolymerized as a monomer, the resulting fluorine-containing resin is excellent in water resistance and hydrophobicity, and that a coating layer formed by copolymerizing an alkyl (meth) acrylate and a hydantoin epoxy resin with an inorganic substance can maintain excellent superhydrophobic performance for a long time in an environment of high temperature, high humidity and high salinity.

After the super-hydrophobic coating is applied to the electrical cabinet, the coating can be effectively waterproof, moistureproof and condensation-proof, particularly plays a role in high-temperature, high-humidity and high-salinity atmosphere along the south, and ensures that the electrical cabinet does not absorb water vapor for corrosion.

Drawings

FIG. 1 shows the superhydrophobic effect of the surface of the electrical cabinet after the two-component superhydrophobic coating is treated.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only some embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

The reagents used in the present invention are all conventional reagents commercially available unless otherwise specified.

In the examples of the present invention, "part(s)" means part(s) by mass unless otherwise specified.

The hydantoin epoxy resin is purchased from Shanghai science and technology Limited, Wuhan, with an epoxy value of 0.58 and a viscosity of 30000 MPS. The itaconic acid based epoxy resin was purchased from Ningbo materials eye residence of Chinese academy of sciences, and had an epoxy value of 0.62 and a viscosity of 5000 MPS. White carbon black is purchased from Wacker (WACKER), is N20 in type, and has a specific surface area of 200m²(ii) in terms of/g. The hydrophobic heavy calcium powder, namely stearic acid modified heavy calcium powder, is purchased from Suzhou Shenba fine chemical Co., Ltd, has the granularity of 2300 meshes and the model of NM-97, and is nano-sized.

Preparation examplePreparation of fluorine-containing acrylic acid-based resin

Preparation example 1

Adding 120g of acrylic acid derivative monomer butyl methacrylate, 65g of acrylic acid- (undecyloxypentyloxy phenyl) ethyl ester (corresponding to the compound in the formula I, n is 2, m is 4) and 5g of itaconic acid group epoxy resin into 600m L ethyl acetate, adding 1g of azobisisobutyronitrile, stirring and reacting for 15-20 hours under the condition of nitrogen and heating reflux at 80 ℃, after the reaction is finished, adding 500m of precipitating agent of L methanol and water (v/v is 4:1) into the reaction liquid for precipitation, performing suction filtration, continuing to precipitate the filtrate by using 300m of precipitating agent of L methanol and water (v/v is 4:1), combining the two precipitates, performing vacuum drying and grinding to obtain the fluorine-containing acrylic acid group resin, which is hereinafter referred to as fluorine-containing resin 1.

Preparation example 2

The operation and conditions were the same as in production example 1 except that the amounts of the monomers were changed to 150g of butyl methacrylate, 75g of- (undecafluoropentyloxyphenyl) ethyl acrylate and 5g of itaconic acid based epoxy resin to obtain a fluorine-containing acrylic acid based resin, hereinafter referred to as fluorine-containing resin 2.

Preparation example 3

The operation and conditions were the same as in production example 1 except that the amounts of the monomers used were changed to 100g of butyl methacrylate, 40g of- (undecafluoropentyloxyphenyl) ethyl acrylate and 6.5g of itaconic acid based epoxy resin to obtain a fluorine-containing acrylic acid based resin, hereinafter referred to as fluorine-containing resin 3.

Preparation example 4

The operation and conditions were the same as in production example 1 except that the amounts of the monomers were changed to 180g of butyl methacrylate, 80g of- (undecafluoropentyloxyphenyl) ethyl acrylate and 5g of itaconic acid based epoxy resin to obtain a fluorine-containing acrylic acid based resin, hereinafter referred to as fluorine-containing resin 4.

Preparation example 5

The operation and conditions were the same as in production example 1 except that the amounts of the monomers used were changed to 120g of butyl methacrylate, 65g of- (undecafluoropentyloxyphenyl) ethyl acrylate and 3.5g of itaconic acid based epoxy resin to obtain a fluorine-containing acrylic acid based resin, hereinafter referred to as fluorine-containing resin 5.

Preparation example 6

The operation and conditions were the same as in production example 1 except that the amounts of the monomers were changed to 120g of butyl methacrylate, 35g of- (undecafluoropentyloxyphenyl) ethyl acrylate and 5g of itaconic acid based epoxy resin to obtain a fluorine-containing acrylic acid based resin, hereinafter referred to as fluorine-containing resin 6.

Preparation example 7

The operation and conditions were the same as in production example 1 except that the amounts of the monomers were changed to 120g of butyl methacrylate, 65g of- (undecafluoropentyloxyphenyl) ethyl acrylate and 10g of itaconic acid based epoxy resin to obtain a fluorine-containing acrylic acid based resin, hereinafter referred to as fluorine-containing resin 7.

Preparation example 8

The operation and conditions were the same as in preparation example 1 except that ethyl- (undecafluoropentyloxyphenyl) acrylate was replaced with ethyl- (tridecafluorohexylphenyl) acrylate (corresponding to the compound of formula I, n is 2, and m is 5) to obtain a fluorine-containing acrylic acid based resin, hereinafter referred to as a fluorine-containing resin 8.

Preparation example 9

The operation and conditions were the same as in preparation example 1 except that the ethyl- (undecafluoropentyloxyphenyl) acrylate was replaced with ethyl- (nonafluorobutoxyphenyl) acrylate (corresponding to the compound of formula I, n was 2, and m was 3) to obtain a fluorine-containing acrylic acid based resin, hereinafter referred to as a fluorine-containing resin 9.

Preparation example 10

The operation and conditions were the same as those in preparation example 1 except that the amount of the monomers was changed to 120g of acrylic acid derivative monomers alkyl (meth) acrylate, 65g of- (undecafluoropentyloxyphenyl) ethyl acrylate, that is, no itaconic acid based epoxy resin was added. Finally, a fluorine-containing acrylic resin, hereinafter referred to as a fluorine-containing resin 10, is obtained.

Comparative preparation example 1

The operation and conditions were the same as in production example 1 except that ethyl- (undecafluoropentyloxyphenyl) acrylate was replaced with dodecafluoroheptyl methacrylate to obtain a fluorine-containing acrylic acid based resin, hereinafter referred to as fluorine-containing resin 11.

Comparative preparation example 2

The operation and conditions were the same as in production example 1 except that ethyl- (undecafluoropentyloxyphenyl) acrylate was replaced with hexafluorobutyl acrylate to obtain a fluorine-containing acrylic acid based resin, hereinafter referred to as fluorine-containing resin 12.

Comparative preparation example 3

The operation and conditions were the same as in preparation example 1 except that ethyl- (undecafluoropentyloxyphenyl) acrylate was replaced with dodecyl acrylate to obtain an acrylic-based resin, hereinafter referred to as resin A.