Anti-icing paints and coatings, and anti-fouling paints and coatings

Abstract

The present invention relates to an anti-icing paint and coating film, and the anti-icing paint of the present invention comprises the following components (A) to (E): Component (A) Paint resin 20~40% by mass Component (B) Porous filler 10 to 30% by mass Component (C) Hydrophobic auxiliary 2 to 20% by mass Component (D) Wax having a melting point of 60 to 160°C: 1 to 10% by mass Component (E) Organic solvent Balance In the coating material of the present invention, component (A) may be a modified polymer having a main chain composed of (a) a fluorine-containing polymer and side chains based on monomers represented by general formulas (b) and (c). CH2=C(-R1)-C(=O)-O-Si(-CH3)2-[O-Si(-CH3)2]nO-Si(-CH3)2-R2 (b) CH2=C(-R3)-C(=O)-XY (c) Furthermore, the present invention relates to an antifouling paint and a coating film, and the antifouling paint of the present invention comprises the above-mentioned modified polymer, a curing agent and an organic solvent.

Description

[Technical field]

[0001] The present invention relates to the field of paints, and in particular to anti-icing paints and coatings, and anti-fouling paints and coatings. [Background technology]

[0002] Freezing and condensation are natural phenomena. In general, freezing and condensation are mainly formed by various meteorological factors such as temperature, humidity, convection of cold and hot air, atmospheric circulation, wind speed, etc. However, freezing and condensation are detrimental to wind turbine blades, bridge cables, power systems, heat exchanger fins, etc.

[0003] For example, in the case of a wind power generation system, when the wind power generation blades are exposed to humid air, rain, salt fog, ice, snow, etc. while operating under low temperature conditions, ice is easily formed on the blades, which not only greatly reduces the efficiency of the wind power generator and shortens the life of the blades, but also causes a large area of ​​accumulated ice to fall off, which may cause a major safety hazard. Therefore, the paint used on the wind power generation blades must not only have excellent adhesion, good weather resistance and abrasion resistance, but also have anti-icing and self-cleaning properties.

[0004] Current anti-icing technology can be divided into sacrificial coating and hydrophobic coating based on two aspects: the anti-icing principle and the effect on ice adhesion. Sacrificial coating mainly uses anti-icing agent released from the coating surface to lower the freezing point of water and form a thin water film between the ice and the coating surface, making it difficult for ice to adhere to the coating surface. However, the use of sacrificial coating is greatly limited, it cannot be used for a long time, and needs to be painted periodically. Hydrophobic coating achieves superhydrophobicity by the micro-nano structure of the coating surface, but in low temperature and high humidity environments, when water vapor penetrates the micro-nano structure, rather than achieving the anti-icing effect, the adhesion between the ice layer and the coating becomes stronger, making deicing difficult. Therefore, in low temperature and high humidity environments, the anti-icing effect should be achieved by mainly using sacrificial coating and imparting hydrophobicity to the coating surface.

[0005] Patent Document 1 (Chinese Patent Document with Publication No. CN104449317A) discloses a paint that can prevent snow and ice from being covered, and the paint can reduce snow and ice by combining a low surface energy resin with an anti-icing agent polyethylene glycol to form a hydrophobic coating layer, but when the coating layer is worn out, the anti-icing performance of the coating layer is lost as the anti-icing agent is consumed. Patent Document 2 (Chinese Patent Document with Publication No. CN109722150A) discloses an anti-icing wind power blade and a manufacturing method thereof, and by adding a conductive filler, the freezing point is lowered and the surface temperature of the substrate is raised, effectively delaying the formation of ice crystals and achieving an anti-icing effect, but the coating layer cannot be widely used because of the need for lightning protection. In summary, the currently produced paints and coatings have low surface durability and cannot achieve sustained and efficient anti-icing, and it is expected to develop a more efficient and durable paint. Prior art literature

[0006] Patent document 1: Chinese patent document with publication number CN104449317A

[0007] Patent document 2: Chinese patent document with publication number CN109722150A Summary of the Invention

[0008] The present invention aims to provide a paint and coating film that overcomes the shortcomings of the prior art and can achieve a sustained and efficient anti-icing effect. Another aim of the present invention is to provide a paint and coating film that can achieve a sustained and efficient anti-fouling effect.

[0009] The object of the present invention is achieved by the following technical solutions:

[0010] The first aspect of the present invention relates to a method for producing a composition comprising the following components (A) to (E): Component (A) Paint resin 20~40% by mass Component (B) Porous filler 10 to 30% by mass Component (C) Hydrophobic auxiliary 2 to 20% by mass Component (D) Wax having a melting point of 60 to 160°C: 1 to 10% by mass Component (E) Organic solvent Balance The present invention relates to a paint comprising:

[0011] In the present invention, on the one hand, the durability of the anti-icing effect is improved by the synergistic effect between the hydrophobic auxiliary (C) and the porous filler (B), and on the other hand, the durability of the anti-icing effect is further improved by the synergistic effect between the wax (D) having a melting point of 60 to 160°C) and the hydrophobic auxiliary (C).

[0012] In the present invention, the coating resin, component (A), is preferably at least one selected from hydroxyacrylic resins, polyester resins, silicone resins, fluorocarbon resins, and fluorosilicone resins, and is more preferably a fluorosilicone resin.

[0013] In the present invention, the component (A) may be the modified polymer (A') described below. The modified polymer (A') is A main chain composed of a fluorine-containing polymer; and side chains based on monomers represented by general formulas (b) and (c). CH2=C(-R1)-C(=O)-O-Si(-CH3)2-[O-Si(-CH3)2]nO-Si(-CH3)2-R2 (b) (In the formula, R1 is a hydrogen atom or a methyl group, R2 is a hydrogen atom or a methyl group, and n is 3 to 200.) CH2=C(-R3)-C(=O)-XY (c) (In the formula, R3 is a hydrogen atom or a methyl group, X is O or N, and Y is one group selected from a linear alkyl group, a cyclic alkyl group, a hydroxyl group, an amino group, a carboxyl group, an amide group, and an epoxy group.)

[0014] In the present invention, the component (B) porous filler is preferably a porous filler having a porosity of 30% or more, more preferably one or more selected from silica, graphite, diatomaceous earth, mica powder, kaolin, calcium carbonate, titanium dioxide, zinc oxide, quartz powder, and barium sulfate, and even more preferably one or more selected from silica, kaolin, and calcium carbonate.

[0015] In the present invention, the hydrophobic auxiliary component (C) is preferably one or more selected from acrylates, fluorine-containing acrylates, silicon-containing acrylates, dimethylsilicone oils, hydroxysilicone oils, aminosilicone oils, perfluoroalkanes, and perfluoropolyethers, and the hydrophobic auxiliary component (C) more preferably has a weight average molecular weight of 2,000 to 50,000.

[0016] In the present invention, the mass ratio (B) / (C) of the content of component (B) to the content of component (C) is preferably 0.9 to 9.4, more preferably 1.1 to 8.6, and even more preferably 3.0 to 6.5.

[0017] In the present invention, the mass ratio of the total content of component (B) and content of component (C) to the content of component (D), [(B)+(C)] / (D), is preferably 2.4-23.6, more preferably 7-20.

[0018] In the present invention, the wax having a melting point of 60 to 160° C. as component (D) is preferably one or more waxes selected from paraffin wax, polyoxyethylene wax, polyethylene wax, polypropylene wax, polyamide wax, and polytetrafluoroethylene wax.

[0019] The second aspect of the present invention relates to a coating film obtained by applying the coating material of the first aspect of the present invention. The coating film of the second aspect of the present invention has an initial contact angle with water of 95° to 110°. And / or the coating film of the present invention has a contact angle with water of 95° to 135° after 3000 hours of ultraviolet aging by exposure to artificial radiation.

[0020] Furthermore, a third aspect of the present invention relates to the use of the paint of the first aspect for anti-icing, preferably using the paint of the present invention on wind turbine blades, bridge lock cables, power systems, and heat exchanger fins.

[0021] A fourth aspect of the present invention relates to a modified polymer, which is the above modified polymer (A').

[0022] In the modified polymer according to the fourth aspect of the present invention, the (a) fluorine-containing polymer preferably contains polymerized units based on tetrafluoroethylene or chlorotrifluoroethylene.

[0023] A fifth aspect of the present invention relates to a coating material comprising the modified polymer according to the fourth aspect of the present invention, a curing agent and an organic solvent.

[0024] A sixth aspect of the present invention relates to a coating film obtained by applying the coating material according to the fifth aspect of the present invention.

[0025] A seventh aspect of the present invention relates to the use of a paint according to the fifth aspect of the present invention in antifouling. Effect of the Invention

[0026] The first-side paint and the second-side coating film of the present invention have good anti-icing effect and can maintain this good anti-icing effect for a long period of time, and can be widely applied in fields such as wind power blades, bridge lock cables, power systems, and heat exchanger fins. The fifth-side paint and the sixth-side coating film of the present invention can achieve a long-lasting excellent anti-fouling effect. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0027] In order to make the technical problems to be solved, the technical solutions and the beneficial effects of the present invention clearer, the present invention will be described in more detail below. It should be understood that the specific examples are only for illustrating the present invention and are not intended to limit the present invention.

[0028] The first aspect of the present invention relates to a method for producing a composition comprising the following components (A) to (E): Component (A) Paint resin 20~40% by mass Component (B) Porous filler 10 to 30% by mass Component (C) Hydrophobic auxiliary 2 to 20% by mass Component (D) Wax having a melting point of 60 to 160°C: 1 to 10% by mass Component (E) Organic solvent Balance The present invention relates to a paint (hereinafter, sometimes simply referred to as "paint I") characterized by containing the above. <Component (A)>

[0029] The component (A) of the present invention is a coating resin, and is not particularly limited as long as it is a resin that has been conventionally used in the coating field. The coating resin of component (A) may be one or more selected from hydroxyacrylic resin, polyester resin, silicone resin, fluorocarbon resin, and fluorosilicone resin, among which silicone resin, fluorocarbon resin, and fluorosilicone resin are preferred, and fluorosilicone resin is more preferred.

[0030] In the present invention, in order to ensure that the coating film prepared by the anti-ice coating paint has good performance in terms of adhesion, abrasion resistance, weather resistance and chemical resistance, the hydroxyacrylic resin has a hydroxyl group content (mass%) of 2-5 mass%, a resin solid content (mass%) of 65-80 mass%, a glass transition temperature of -40-10°C and a flexibility of ≦1 mm, when the mass of the hydroxyacrylic resin is 100%. Furthermore, the hydroxyacrylic resin is preferably a polyurethane-modified hydroxyacrylic resin, or the hydroxyacrylic resin is one of the composites formed by the hydroxyacrylic resin, the fluorine-containing acrylic resin and the silicon-containing acrylic resin.

[0031] In the present invention, polyester resins are divided into saturated polyesters and unsaturated polyesters. Saturated polyesters refer to those whose synthetic raw materials do not contain unsaturated bonds other than benzene rings. The polyester resins used in the present invention are low molecular weight, amorphous, crosslinkable polymers containing branched chains, and are formed by esterifying polyhydric alcohols and polybasic acids. They have two structures, a pure linear structure and a branched structure. Paint films prepared with resins having a pure linear structure have good flexibility and processing performance, while paint films prepared with resins having a branched structure have excellent hardness and weather resistance. By adjusting the composition of the polyester resin, for example, by making the polyol excessive, a hydroxyl-terminated polyester can be obtained, and when the acid is excessive, a carboxyl-terminated polyester can be obtained. In the present invention, the polyester resin used as the component (A) paint resin is more preferably an unsaturated polyester resin. The unsaturated polyester resin is a polyester resin containing a terminal hydroxyl functional group, and is formed into a film by crosslinking and curing with resins such as isocyanate and amino resin.

[0032] In the present invention, examples of silicone resins include polyalkyl silicone resins, polyaryl silicone resins, and polyalkylaryl silicone resins. Monomers for synthesizing silicone resins are divided into organic chlorosilane monomers, organic alkoxysilane monomers, organic acyloxysilane monomers, organic silanols, and silicone monomers containing organic functional groups, depending on the type of functional group. In the present invention, the silicone resin as component (A) coating resin is preferably a silicone resin prepared by copolymerization of dichlorosilane and trichlorosilane.

[0033] In the present invention, examples of the fluorocarbon resin include polytetrafluoroethylene (PTFE), polychlorotrifluoroethylene (PCTFE), polyvinyl fluoride (PVF), polyvinylidene fluoride (PVDF), polyperfluoropropylene (FEP), ethylene-tetrafluoroethylene copolymer (ETFE), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), ethylene-chlorotrifluoroethylene copolymer (ECTFE), fluoroolefin-vinyl ether copolymer (FEVE), etc. In the present invention, the fluorocarbon resin as the component (A) coating resin is preferably fluoroolefin-vinyl ether copolymer (FEVE).

[0034] In the present invention, fluorosilicone resin refers to a resin formed by polymerizing a fluorine-containing monomer and a silicon-containing monomer. Depending on the position of the fluorosilicone monomer, it is divided into three types: fluorine main chain silicon side chain, silicon main chain fluorine side chain, and fluorine silicon main chain polymerization. From the viewpoint of improving weather resistance and hydrophobicity, the two types of fluorine main chain silicon side chain and fluorine silicon main chain polymerization are preferred.

[0035] Combining silicone resin with fluorocarbon resin produces fluorosilicone resin, which has better corrosion resistance, impact resistance, high and low temperature resistance, water repellency and oil repellency, and can improve the problems of silicone resin such as adhesion, film formation, curing temperature, and cost of organic fluorine.

[0036] According to the polymerization mechanism, the synthesis of fluorosilicone resin can be divided into two types: chain polymerization and gradual polymerization. Chain polymerization can be divided into free radical polymerization and ionic polymerization according to the method of breaking the covalent bond. Fluorosilicone resin synthesized by free radical has many monomers, and when fluorine-containing acrylic acid, tetrafluoroethylene, alkoxysilane, etc. are used as monomers, water-soluble, solvent-based, and emulsion-based fluorosilicone resins can be prepared. The modes of ionic polymerization include anionic, cationic polymerization, and coordination polymerization. Anionic and cationic polymerization can obtain polymers with narrow molecular weight distribution. The gradual polymerization reaction mainly involves condensing fluorine-containing silane or fluorine-containing siloxane to obtain fluorosilicone polymer, and then reacting with acrylic ester to obtain fluorosilicone acrylate polymer.

[0037] In the present invention, component (A) is (a) a main chain composed of a fluorine-containing polymer; The modified polymer (A') may have side chains based on monomers represented by general formulas (b) and (c). CH2=C(-R1)-C(=O)-O-Si(-CH3)2-[O-Si(-CH3)2]nO-Si(-CH3)2-R2 (b) (In the formula, R1 is a hydrogen atom or a methyl group, R2 is a hydrogen atom or a methyl group, and n is 3 to 200.) CH2=C(-R3)-C(=O)-XY (c) (In the formula, R3 is a hydrogen atom or a methyl group, X is O or N, and Y is one group selected from a linear alkyl group, a cyclic alkyl group, a hydroxyl group, an amino group, a carboxyl group, an amide group, and an epoxy group.) <Main chain>

[0038] The modified polymer of the present invention has (a) a main chain composed of a fluorine-containing polymer.

[0039] Fluorine-containing resins are well known as resins excellent in heat resistance, chemical resistance, weather resistance, etc. The modified polymer of the present invention has specific side chains, and in addition to the excellent heat resistance, chemical resistance, weather resistance, etc. that fluorine-containing polymers inherently have, it can obtain an excellent antifouling effect that lasts for a long period of time.

[0040] The fluorine-containing polymer preferably contains a unit represented by -CHR- (wherein R is a hydrogen atom or a monovalent organic group). -CHR- is bonded to the main chain, and at least one -CHR- may be present. The fluorine-containing polymer preferably contains a polymerization unit that is -CH2-CHR-.

[0041] In the unit represented by -CHR-, R is a hydrogen atom or a monovalent organic group.

[0042] Examples of the monovalent organic group include an alkyl group which may have one or more substituents, an alkenyl group which may have one or more substituents, an alkynyl group which may have one or more substituents, a cycloalkyl group which may have one or more substituents, a cycloalkenyl group which may have one or more substituents, a cyclodienyl group which may have one or more substituents, an aryl group which may have one or more substituents, an aralkyl group which has one or more substituents, a non-aromatic heterocyclic group which may have one or more substituents, a heteroaryl group which may have one or more substituents, a cyano group, an acyl group, RaO-, RaCO-, RaSO2-, RaCOO-, RaNRaCO-, RaCONRa-, RaOCO-, RaOSO 2- and RaNRbSO2- (in these formulas, Ra is independently an alkyl group which may have one or more substituents, an alkenyl group which may have one or more substituents, an alkynyl group which may have one or more substituents, a cycloalkyl group which may have one or more substituents, a cycloalkenyl group which may have one or more substituents, a cyclodienyl group which may have one or more substituents, an aryl group which may have one or more substituents, an aralkyl group which has one or more substituents, a non-aromatic heterocyclic group which may have one or more substituents, or a heteroaryl group which may have one or more substituents; and Rb is independently H or an alkyl group which may have one or more substituents).

[0043] The organic group is preferably an alkyl group having one or more substituents.

[0044] In the present specification, the term "substituent" refers to a substitutable group. Examples of the "substituent" include an aliphatic group, an aromatic group, a heterocyclic group, an acyl group, an acyloxy group, an amide group, an aliphatic oxy group, an aromatic oxy group, a heterocyclic oxy group, an aliphatic oxycarbonyl group, an aromatic oxycarbonyl group, a heterocyclic oxycarbonyl group, a carbamoyl group, an aliphatic sulfonyl group, an aromatic sulfonyl group, a heterocyclic sulfonyl group, an aliphatic sulfonyloxy group, an aromatic sulfonyloxy group, a heterocyclic sulfonyloxy group, a sulfamoyl group, an aliphatic sulfonamide group, an aromatic sulfonamide group, a heterocyclic sulfonamide group, an amino group, and an aliphatic amino group. , aromatic amino groups, heterocyclic amino groups, aliphatic oxycarbonylamino groups, aromatic oxycarbonylamino groups, heterocyclic oxycarbonylamino groups, aliphatic sulfinyl groups, aromatic sulfinyl groups, aliphatic thio groups, aromatic thio groups, hydroxyl groups, cyano groups, sulfo groups, carboxyl groups, aliphatic oxygen amino groups, aromatic oxyamino groups, carbamoylamino groups, sulfamoylamino groups, halogen atoms, sulfamoylcarbamoyl groups, carbamoylsulfamoyl groups, biphasic oxyphosphinyl groups and biaromatic oxyphosphinyl groups.

[0045] The aliphatic group may be saturated or unsaturated and may have a hydroxyl group, an aliphatic oxy group, a carbamoyl group, an aliphatic oxycarbonyl group, an aliphatic thio group, an amino group, an aliphatic amino group, an amido group, a carbamoylamino, etc. Examples of the aliphatic group include alkyl groups having a total of 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms, such as a methyl group, an ethyl group, a vinyl group, a cyclohexyl group, and a carbamoylmethyl group.

[0046] The aromatic group may have, for example, a nitro group, a halogen atom, an aliphatic oxy group, a carbamoyl group, an aliphatic oxycarbonyl group, an aliphatic thio group, an amino group, an aliphatic amino group, an acylamino group, a carbamoylamino group, etc. Examples of the aromatic group include aryl groups having a total of 6 to 12 carbon atoms, preferably 6 to 10 carbon atoms, such as a phenyl group, a 4-nitrophenyl group, a 4-acetylaminophenyl group, and a 4-methanesulfonylphenyl group.

[0047] The heterocyclic group may have a halogen atom, a hydroxyl group, an aliphatic oxy group, a carbamoyl group, an aliphatic oxycarbonyl group, an aliphatic thio group, an amino group, an aliphatic amino group, an acylamino group, a carbamoylamino group, etc. Examples of the heterocyclic group include 5- or 6-membered heterocyclic rings having a total of 2 to 12, preferably 2 to 10, carbon atoms, such as 2-tetrahydrofuranyl and 2-pyrimidinyl.

[0048] The acyl group may have an aliphatic carbonyl group, an arylcarbonyl group, a heterocyclic carbonyl group, a hydroxyl group, a halogen atom, an aromatic group, an aliphatic oxy group, a carbamoyl group, an aliphatic oxycarbonyl group, an aliphatic thio group, an amino group, an aliphatic amino group, an acylamino group, a carbamoylamino group, etc. Examples of the acyl group include acyl groups having a total of 2 to 8 carbon atoms, preferably 2 to 4 carbon atoms, such as an acetyl group, a propionyl group, a benzoyl group, and a 3-pyridinecarbonyl group.

[0049] The acylamino group may have an aliphatic group, an aromatic group, a heterocyclic group, etc., such as an acetylamino group, a benzoylamino group, a 2-pyridinecarbonylamino group, a propionylamino group, etc. Examples of the acylamino group include acylamino groups having a total of 2 to 12 carbon atoms, preferably 2 to 8 carbon atoms, such as alkylcarbonylamino groups having a total of 2 to 8 carbon atoms, such as an acetylamino group, a benzoylamino group, a 2-pyridinecarbonylamino group, a propionylamino group, etc.

[0050] The aliphatic oxycarbonyl group may be saturated or unsaturated and may have a hydroxyl group, an aliphatic oxy group, a carbamoyl group, an aliphatic oxycarbonyl group, an aliphatic thio group, an amino group, an aliphatic amino group, an amido group, a carbamoylamino, etc. Examples of the aliphatic oxycarbonyl group include alkoxycarbonyl groups having a total of 2 to 8 carbon atoms, preferably 2 to 4 carbon atoms, such as a methoxycarbonyl group, an ethoxycarbonyl group, a (tert)butoxycarbonyl group, etc.

[0051] The carbamoyl group may have an aliphatic group, an aromatic group, a heterocyclic group, etc. Examples of the carbamoyl group include an unsubstituted carbamoyl group and an alkylcarbamoyl group having a total of 2 to 9 carbon atoms, and an unsubstituted carbamoyl group, for example, an alkylcarbamoyl group having a total of 2 to 5 carbon atoms such as N-methylcarbamoyl, N,N-dimethylcarbamoyl, N-phenylcarbamoyl, etc., is preferred.

[0052] The aliphatic sulfonyl group may be saturated or unsaturated and may have a hydroxyl group, an aromatic group, an aliphatic oxy group, a carbamoyl group, an aliphatic oxycarbonyl group, an aliphatic thio group, an amino group, an aliphatic amino group, an amido group, a carbamoylamino group, etc. Examples of the aliphatic sulfonyl group include alkylsulfonyl groups having a total of 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, such as methanesulfonyl.

[0053] The aromatic sulfonyl group may have a hydroxyl group, an aliphatic group, an aliphatic oxy group, a carbamoyl group, an aliphatic oxycarbonyl group, an aliphatic thio group, an amino group, an aliphatic amino group, an acylamino group, a carbamoylamino group, etc. Examples of the aromatic sulfonyl group include arylsulfonyl groups having 6 to 10 carbon atoms, such as a benzenesulfonyl group.

[0054] The amino group may have an aliphatic group, an aromatic group, a heterocyclic group, or the like.

[0055] The acylamino group may have, for example, an acetylamino group, a benzoylamino group, a 2-pyridinecarbonylamino group, a propionylamino group, etc. Examples of the acylamino group include acylamino groups having a total of 2 to 12 carbon atoms, preferably 2 to 8 carbon atoms, and more preferably alkylcarbonylamino groups having a total of 2 to 8 carbon atoms, such as acetylamino, benzoylamino, 2-pyridinecarbonylamino, and propionylamino.

[0056] Examples of the aliphatic sulfonamide group, aromatic sulfonamide group, and heterocyclic sulfonamide group include a methylsulfonamide group, a benzenesulfonamide group, and a 2-pyridinesulfonamide group.

[0057] The sulfamoyl group may have an aliphatic group, an aromatic group, a heterocyclic group, etc. Examples of the sulfamoyl group include a sulfamoyl group, an alkylsulfamoyl group having a total of 1 to 9 carbon atoms, a dialkylsulfamoyl group having a total of 2 to 10 carbon atoms, an arylsulfamoyl group having a total of 7 to 13 carbon atoms, and a heterocyclic sulfamoyl group having a total of 2 to 12 carbon atoms, and more preferably includes a sulfamoyl group, an alkylsulfamoyl group having a total of 1 to 7 carbon atoms, a dialkylsulfamoyl group having a total of 3 to 6 carbon atoms, and an arylsulfamoyl group having a total of 6 to 11 carbon atoms, such as a sulfamoyl group, a methylsulfamoyl group, N,N-dimethylsulfamoyl, a phenylsulfamoyl, and a 4-pyridine sulfamoyl, and other heterocyclic sulfamoyl groups having a total of 2 to 10 carbon atoms.

[0058] The aliphatic oxy group may be saturated or unsaturated and may have a methoxy group, an ethoxy group, an isopropoxy group, a cyclohexyloxy group, a methoxyethoxy group, etc. Examples of the aliphatic oxy group include alkoxy groups having a total of 1 to 8 carbon atoms, preferably 1 to 6 carbon atoms, such as methoxy, ethoxy, isopropoxy, cyclohexyloxy, and methoxyethoxy groups.

[0059] The aromatic amino group and heterocyclic amino group may have an aliphatic group, an aliphatic oxy group, a halogen atom, a carbamoyl group, a heterocyclic group condensed with the aryl group, or an aliphatic oxycarbonyl group, and preferably has an aliphatic group having a total of 1 to 4 carbon atoms, an aliphatic oxy group having a total of 1 to 4 carbon atoms, a halogen atom, a carbamoyl group having a total of 1 to 4 carbon atoms, a nitro group, or an aliphatic oxycarbonyl having a total of 2 to 4 carbon atoms.

[0060] The aliphatic thio group may be saturated or unsaturated, and examples thereof include alkylthio groups having a total of 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms, such as methylthio, ethylthio, carbamoylmethylthio, and tert-butylthio.

[0061] The carbamoylamino group may have an aliphatic group, an aryl group, a heterocyclic group, etc. Examples of the carbamoylamino group include a carbamoylamino group, an alkylcarbamoylamino group having a total of 2 to 9 carbon atoms, a dialkylcarbamoylamino group having a total of 3 to 10 carbon atoms, an arylcarbamoylamino group having a total of 7 to 13 carbon atoms, and a heterocyclic carbamoylamino group having a total of 3 to 12 carbon atoms, and preferably a carbamoylamino group, an alkylcarbamoylamino group having a total of 2 to 7 carbon atoms, a dialkylcarbamoylamino group having a total of 3 to 6 carbon atoms, and an arylcarbamoylamino group having a total of 7 to 11 carbon atoms, such as a heterocyclic carbamoylamino group having a total of 3 to 10 carbon atoms, such as carbamoylamino, methylcarbamoylamino, N,N-dimethylcarbamoylamino, phenylcarbamoylamino, and 4-pyridinecarbamoylamino.

[0062] The above R is preferably a group containing a functional group, and examples of the functional group include a hydroxyl group (however, a hydroxyl group contained in a carboxyl group is not included; the same applies below), a carboxyl group, an ester bond (-OCO-), a group represented by -COOCO-, a cyano group, an amino group, an epoxy group, a silyl group, and the like. Among these, R is preferably at least one group selected from the group consisting of a hydroxyl group, a carboxyl group, an ester bond, a group represented by -COOCO-, an amino group, a cyano group, and a silyl group, more preferably at least one group selected from the group consisting of a hydroxyl group, a carboxyl group, an ester bond, an amino group, and a silyl group, more preferably at least one group selected from the group consisting of a hydroxyl group, a carboxyl group, an ester bond, an amino group, and a silyl group, and particularly preferably at least one group selected from the group consisting of a hydroxyl group, a carboxyl group, an ester bond, and an amino group. Specific examples of the above R include a carboxyl group, -Op-Rdq-OH (wherein Rd is a linear or branched alkylene group having 1 to 10 carbon atoms, p is 0 or 1, and q is 0 or 1), -OCO-Re (wherein Re is a hydrocarbon group having 1 to 10 carbon atoms), etc. The above Re may be a linear or branched hydrocarbon group (e.g., an alkyl group, etc.) or a cyclic hydrocarbon group (e.g., a cycloalkyl group, a phenyl group, etc.).

[0063] The above R is preferably a group containing a curable functional group, and examples of the curable functional group include, for example, a hydroxyl group, a carboxyl group, a group represented by -COOCO-, a cyano group, an amino group, an epoxy group, and a silyl group. Among them, from the viewpoint of good curing reactivity, it is preferably at least one group selected from the group consisting of a hydroxyl group, a carboxyl group, a group represented by -COOCO-, an amino group, a cyano group, and a silyl group, more preferably at least one group selected from the group consisting of a hydroxyl group, a carboxyl group, an amino group, and a silyl group, even more preferably at least one group selected from the group consisting of a hydroxyl group, a carboxyl group, and an amino group, and particularly preferably a group selected from the group consisting of a hydroxyl group and an acarboxyl group. These curable functional groups are usually introduced into the fluorine-containing polymer by copolymerizing a monomer containing a curable functional group.

[0064] Among the above fluorine-containing polymers, the fluorine-containing polymer having a curable functional group is preferred because it has excellent weather resistance. The above fluorine-containing polymer having a curable functional group includes a polymer obtained by introducing a curable functional group into a fluorine-containing polymer. By having the above structure, it is possible to achieve both weather resistance and antifouling properties at a more excellent level.

[0065] Among the above fluorine-containing polymers, it is preferable to use a fluorine-containing monomer unit, a vinyl ester unit not containing either a hydroxyl group or an aromatic ring, and a monomer unit containing a hydroxyl group, because the fluorine-containing polymer has excellent weather resistance and is easily soluble in an ester solvent. By having the above structure, it is possible to achieve both weather resistance and antifouling properties at a more excellent level.

[0066] Examples of the fluorine-containing monomer constituting the fluorine-containing monomer unit include tetrafluoroethylene, chlorotrifluoroethylene, vinylidene fluoride, vinyl fluoride, fluorovinyl ether, and the like, and one or more of these can be used.

[0067] The fluorine-containing monomer is preferably at least one selected from the group consisting of tetrafluoroethylene, chlorotrifluoroethylene, and vinylidene fluoride, and more preferably at least one selected from the group consisting of tetrafluoroethylene and chlorotrifluoroethylene, because of its excellent weather resistance. By having the above-mentioned constitution, it is possible to achieve both weather resistance and antifouling properties at a more excellent level.

[0068] The vinyl ester constituting the vinyl ester unit is preferably a vinyl carboxylate, more preferably at least one selected from the group consisting of vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl caproate, tertiary vinyl carbonate, vinyl laurate, vinyl stearate, and vinyl cyclohexyl carboxylate, more preferably at least one selected from the group consisting of vinyl acetate, tertiary vinyl carbonate, vinyl laurate, vinyl stearate, and vinyl cyclohexyl carboxylate, and particularly preferably at least one selected from the group consisting of vinyl acetate and tertiary vinyl carbonate.

[0069] As the vinyl ester, a carboxylic acid vinyl ester having 6 or more carbon atoms is preferred, and a carboxylic acid vinyl ester having 9 or more carbon atoms is more preferred, because they have better adhesion and abrasion resistance. The upper limit of the carbon number of the carboxylic acid in the carboxylic acid vinyl ester is preferably 20, more preferably 15. Tertiary vinyl carbonates such as vinyl neopergonic acid and vinyl neodecanoic acid are most preferred, because they have better adhesion to the substrate.

[0070] It should be noted that the vinyl ester does not contain any one of a hydroxyl group and an aromatic ring, and preferably does not contain a halogen atom.

[0071] The hydroxyl-containing monomer constituting the hydroxyl-containing monomer unit is preferably at least one selected from the group consisting of hydroxyalkyl vinyl ether, hydroxyalkyl allyl ether, vinyl hydroxycarboxylate, allyl hydroxycarboxylate, and (meth)hydroxyalkyl acrylate, more preferably at least one selected from the group consisting of hydroxyalkyl vinyl ether and hydroxyalkyl allyl ether, and even more preferably hydroxyalkyl vinyl ether.

[0072] Examples of the hydroxyalkyl vinyl ether include 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, 2-hydroxy-2-methylpropyl vinyl ether, 4-hydroxybutyl vinyl ether, 4-hydroxy-2-methylbutyl vinyl ether, 5-hydroxypentyl vinyl ether, and 6-hydroxyhexyl vinyl ether.

[0073] Examples of the hydroxyalkyl allyl ether include 2-hydroxyethyl allyl ether, 4-hydroxybutyl allyl ether, and glycerol monoallyl ether.

[0074] Examples of the vinyl hydroxycarboxylate include vinyl hydroxyacetate, vinyl hydroxypropionic acid, vinyl hydroxybutyrate, vinyl hydroxycaproate, and vinyl 4-hydroxycyclohexyl acetate.

[0075] Examples of the allyl hydroxycarboxylate include allyl hydroxyacetate, allyl hydroxypropionate, allyl hydroxycaproate, and allyl 4-hydroxycyclohexylacetate.

[0076] Examples of the (meth)hydroxyalkyl acrylate include 2-hydroxyethyl acrylate and 2-hydroxyethyl methyl acrylate.

[0077] The alkoxyl group-containing monomer is preferably a monomer represented by the following formula (A): Formula (A): CH2=CH-(CH2)lO-(CH2)m-OH (In the formula, l is 0 or 1, and m is an integer of 2 to 20.) Particularly preferred is at least one monomer selected from the group consisting of 4-hydroxybutyl vinyl ether, 2-hydroxyethyl vinyl ether, 2-hydroxyethyl allyl ether, and 4-hydroxybutyl allyl ether.

[0078] The content of the fluorine-containing monomer unit is preferably 30 to 60 mol %, and more preferably 40 to 55 mol %, based on the total monomer units of the fluorine-containing polymer.

[0079] The content of vinyl ester units not containing either a hydroxyl group or an aromatic ring is preferably from 1 to 40 mol %, more preferably from 10 to 30 mol %, based on the total monomer units of the fluorine-containing polymer.

[0080] The content of the hydroxyl-containing monomer unit is preferably from 15 to 40 mol %, more preferably from 20 to 35 mol %, based on the total monomer units of the fluorine-containing polymer.

[0081] In this specification, the content of each of the monomer units constituting the fluorine-containing polymer can be calculated by appropriately combining NMR, FT-IR, elemental analysis, and X-ray fluorescence analysis depending on the type of monomer.

[0082] The number average molecular weight of the fluorine-containing polymer is preferably 3,000 to 100,000. The number average molecular weight is more preferably 5000 or more, even more preferably 8,000 or more, more preferably 50,000 or less, and even more preferably 35,000 or less. If the number average molecular weight is too small, the weather resistance, solvent resistance, and stain resistance are reduced, and a coating film with high hardness may not be formed. If the number average molecular weight is too large, the viscosity becomes high when the coating film is formed, and handling may be difficult. The number average molecular weight can be measured by gel permeation chromatography (GPC) using tetrahydrofuran as an eluent.

[0083] The glass transition temperature (second heating) of the fluorine-containing polymer determined by differential scanning calorimetry (DSC) is preferably 10 to 70° C., more preferably 15 to 60° C. If the glass transition temperature is too low, the weather resistance, solvent resistance, and stain resistance may decrease, and a coating film with high hardness may not be formed, whereas if the glass transition temperature is too high, the viscosity may become high when a coating film is formed, making it difficult to handle.

[0084] From the viewpoint of good compatibility with polyisocyanate compounds, pigments, etc., the acid value of the fluorine-containing polymer is preferably 0.6 to 50 mgKOH / g, more preferably 2 to 30 mgKOH / g.

[0085] The fluorine-containing polymer may further contain a fluorine-containing monomer unit, a vinyl ester unit not containing either a hydroxyl group or an aromatic ring, and a monomer unit other than the hydroxyl-containing monomer unit. For example, the fluorine-containing polymer may contain a carboxylic acid vinyl ester unit containing an aromatic ring but not containing a hydroxyl group, a carboxyl group-containing monomer, an amino group-containing monomer, a hydrolyzable silyl group-containing monomer, an alkyl vinyl ether not containing a hydroxyl group, an olefin not containing a halogen atom or a hydroxyl group, and the like. The content of these monomer units may be 0 to 10 mol%, preferably 0.1 to 5 mol%, more preferably 0.5 to 3 mol% based on the total monomer units of the fluorine-containing polymer.

[0086] Examples of the vinyl carboxylate having an aromatic ring but no hydroxyl group include vinyl benzoate and vinyl p-tert-butyl benzoate.

[0087] The carboxyl group-containing monomer is preferably a monomer represented by the following formula (B): Formula (B): R1aR2aC=CR3a-(CH2)n-COOH (In the formula, R1a, R2a, and R3a are the same or different and each is a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms, and n is an integer of 0 or more.) Examples include acrylic acid, methacrylic acid, vinylacetic acid, crotonic acid, pentenoic acid, hexenoic acid, heptenoic acid, octenoic acid, nonenoic acid, decenoic acid, undecylenic acid, dodecenoic acid, carbene acid, tridecenoic acid, tetradecenoic acid, pentadecenoic acid, hexadecenoic acid, heptadecenoic acid, octadecenoic acid, nonadecenoic acid, eicosenoic acid, 22-tricosenoic acid, and the like. Of these, at least one selected from the group consisting of acrylic acid, crotonic acid, and undecylenic acid is preferred, and at least one selected from the group consisting of acrylic acid and crotonic acid is more preferred.

[0088] Examples of the carboxyl group-containing monomer include cinnamic acid, 3-allyloxypropionic acid, itaconic acid, itaconic acid monoester, maleic acid, maleic acid monoester, maleic anhydride, fumaric acid, fumaric acid monoester, phthalic acid vinyl ester, vinylpyromellitic acid, citraconic acid, mesaconic acid, and aconitic acid.

[0089] Examples of amino group-containing monomers include aminovinyl ethers represented by CH2=CH-O-(CH2)x-NH2 (x=0 to 10), amines represented by CH2=CH-O-CO(CH2)x-NH2 (x=1 to 10), aminomethylstyrene, vinylamine, acrylamide, vinylacetamide, and vinylformamide.

[0090] Examples of the hydrolyzable silyl group-containing monomer include CH2=CHCO2(CH2)3Si(OCH3)3, CH2=CHCO2(CH2)3Si(OC2H5)3, CH2=C(CH3)CO2(CH2)3Si(OCH3)3, CH2=C(CH3)CO2(CH2)3Si(OC2H5)3, CH2=CHCO2(CH2)3SiCH3(OC2H5)2, CH2=C(CH3)CO2(CH2)3SiC2H5(OCH3)2, CH2=C(CH3)CO2(CH2)3Si(CH3)2(OC2H5), CH2=C(CH3)CO2(CH2)3Si(CH3)2OH, CH2=CH(CH2)3Si(OCOCH3)3, CH2=C(CH3)CO2(CH2)3SiC2H5(OCOCH3)2, CH2=C(CH3)CO2(CH2)3SiCH3(N(CH3)COCH3)2, CH2=CHCO2(CH2)3SiCH3[ON(CH3)C2H5]2, (Meth)acrylates such as CH2=C(CH3)CO2(CH2)3SiC6H5[ON(CH3)C2H5]2; CH2=CHSi[ON=C(CH3)(C2H5)]3, CH2=CHSi(OCH3)3, CH2=CHSi(OC2H5)3, CH2=CHSiCH3(OCH3)2, CH2=CHSi(OCOCH3)3, CH2=CHSi(CH3)2(OC2H5), CH2=CHSi(CH3)2SiCH3(OCH3)2, Vinyl silanes such as CH2=CHSiC2H5(OCOCH3)2, CH2=CHSiCH3[ON(CH3)C2H5]2, vinyltrichlorosilane or partial hydrolysates thereof; and vinyl ethers such as trimethoxysilylethyl vinyl ether, triethoxysilylethyl vinyl ether, trimethoxysilylbutyl vinyl ether, methyldimethoxysilylethyl vinyl ether, trimethoxysilylpropyl vinyl ether, and triethoxysilylpropyl vinyl ether.

[0091] Examples of the alkyl vinyl ether not containing a hydroxyl group include methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, n-butyl vinyl ether, octadecyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexyl vinyl ether, isopropyl vinyl ether, and isobutyl vinyl ether. Among these, at least one selected from the group consisting of ethyl vinyl ether and cyclohexyl vinyl ether is preferred.

[0092] The olefins include non-fluorinated olefins such as ethylene, propylene, n-butene, and isobutene.

[0093] The hydroxyl value of the fluorine-containing polymer is preferably 50 mgKOH / g or more. The hydroxyl value is more preferably 55 mgKOH / g or more, even more preferably 60 mgKOH / g or more, even more preferably 80 mgKOH / g or more, particularly preferably 100 mgKOH / g or more, and is preferably 180 mgKOH / g or less, more preferably 170 mgKOH / g or less, more preferably 160 mgKOH / g or less, particularly preferably 150 mgKOH / g or less.

[0094] The hydroxyl value is calculated from the weight of the fluorine-containing polymer and the number of moles of --OH groups. The number of moles of --OH groups can be determined by NMR measurement, IR measurement, titration, elemental analysis, or the like.

[0095] The above-mentioned fluorine-containing polymer can be produced by any one of solution polymerization, emulsion polymerization, suspension polymerization and bulk polymerization methods, among which the polymer obtained by solution polymerization method is preferred.

[0096] The fluorine-containing polymer is preferably produced by polymerizing a monomer that provides the above units by a solution polymerization method using an organic solvent or a polymerization initiator. The polymerization temperature is usually 0 to 150° C., preferably 5 to 95° C. The polymerization pressure is usually 0.1 to 10 MPaG (1 to 100 kgf / cm2G).

[0097] Examples of the organic solvent include esters such as methyl acetate, ethyl acetate, propyl acetate, n-butyl acetate, and tert-butyl acetate; ketones such as acetone, methyl ethyl ketone, and cyclohexanone; aliphatic hydrocarbons such as hexane, cyclohexane, octane, nonane, decane, undecane, dodecane, and mineral essential oil; aromatic hydrocarbons such as benzene, toluene, xylene, naphthalene, and solvent naphtha; alcohols such as methanol, ethanol, tert-butanol, isopropanol, and ethylene glycol monoalkyl ether; cyclic ethers such as tetrahydrofuran, tetrahydropyran, and dioxane; dimethyl sulfoxide, and the like, or mixtures thereof.

[0098] Examples of the polymerization initiator include persulfates such as ammonium persulfate and potassium persulfate (which may be used in combination with reducing agents such as sodium bisulfite, sodium metabisulfite, cobalt naphthenate, and dimethylaniline, if necessary); redox initiators composed of an oxidizing agent (e.g., ammonium peroxide, potassium peroxide, etc.), a reducing agent (e.g., sodium sulfite, etc.) and a transition metal salt (e.g., iron sulfate, etc.); diacyl peroxides such as acetyl peroxide and benzoyl peroxide; dialkoxycarbonyl peroxides such as isopropoxycarbonyl peroxide and tert-butoxycarbonyl peroxide; ketone peroxides such as methyl ethyl ketone peroxide and cyclohexanone peroxide; and hydrogen peroxide. hydroperoxides such as tert-butyl hydroperoxide and cumene hydroperoxide, dialkyl peroxides such as di-tert-butyl peroxide and dicumyl peroxide; alkyl peroxide esters such as tert-butyl peroxyacetate and tert-butyl peroxypivalate; and azo compounds such as 2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2-methylvaleronitrile), 2,2'-azobis(2-cyclopropylpropionitrile), 2,2'-azobisisobutyrate dimethyl, 2,2'-azobis[2-(hydroxymethyl)propionitrile], and 4,4'-azobis(4-cyanopentenoic acid). <Side chain>

[0099] The modified polymer of the present invention has side chains based on monomers represented by general formulas (b) and (c). CH2=C(-R1)-C(=O)-O-Si(-CH3)2-[O-Si(-CH3)2]nO-Si(-CH3)2-R2 (b) (In the formula, R1 is a hydrogen atom or a methyl group, R2 is a hydrogen atom or a methyl group, and n is 3 to 200.) CH2=C(-R3)-C(=O)-XY (c) (In the formula, R3 is a hydrogen atom or a methyl group, X is O or N, and Y is one group selected from a linear alkyl group, a cyclic alkyl group, a hydroxyl group, an amino group, a carboxyl group, an amide group, and an epoxy group.) In the general formula (b), n is 3-200, preferably 5-200, and more preferably 9-200.

[0100] The side chain based on the monomer represented by formula (b) may have a low molecular weight or a high molecular weight. From the viewpoint of compatibility, a low molecular weight is preferable. In the case of a low molecular weight, n is preferably 3 to 100, more preferably 5 to 80, and even more preferably 9 to 70. From the viewpoint of soil resistance, particularly water repellency and oil repellency, a high molecular weight is preferable. In the case of a high molecular weight, n is preferably 100 to 200, more preferably 120 to 200, and even more preferably 140 to 200.

[0101] Specific examples of the side chain based on the monomer represented by general formula (b) include the structures shown below, but are not limited to these examples. -CH2-CH2-C(=O)-O-Si(-CH3)2-[O-Si(-CH3)2]nO-Si(-CH3)2-H -CH2-CH2-C(=O)-O-Si(-CH3)2-[O-Si(-CH3)2]nO-Si(-CH3)2-CH3 -CH2-CH(-CH3)-C(=O)-O-Si(-CH3)2-[O-Si(-CH3)2]nO-Si(-CH3)2-H -CH2-CH(-CH3)-C(=O)-O-Si(-CH3)2-[O-Si(-CH3)2]nO-Si(-CH3)2-CH3 In formula (c), Y is one group selected from a linear alkyl group, a cyclic alkyl group, a hydroxyl group, an amino group, a carboxyl group, an amide group, and an epoxy group. An example of the linear alkyl group is, for example, a linear alkyl group having 1 to 20 carbon atoms, and an example of the cyclic alkyl group is, for example, a cycloalkyl group having 1 to 20 carbon atoms.

[0102] Specific examples of the side chain based on the monomer represented by general formula (c) include the structures below, but are not limited to these examples. -CH2-CH2-C(=O)-O-(CH2)2-H -CH2-CH2-C(=O)-O-(CH2)2-OH -CH2-CH2-C(=O)-O-(CH2)2N(-CH3)SO2-H -CH2-CH2-C(=O)-O-(CH2)2N(-C2H5)SO2-H -CH2-CH2-C(=O)-O-CH2CH(-OH)CH2-H -CH2-CH2-C(=O)-O-CH2CH(-OCOCH3)CH2-H -CH2-CH2-C(=O)-O-(CH2)2-COOH -CH2-CH2-C(=O)-O-(CH2)2-NH2 -CH2-CH2-C(=O)-O-(CH2)3-SO2-H -CH2-CH2-C(=O)-O-(CH2)2-SO2-(CH2)2-H -CH2-CH2-C(=O)-NH-(CH2)2-H -CH2-CH(-CH3)-C(=O)-O-(CH2)2-H -CH2-CH(-CH3)-C(=O)-O-(CH2)2-OH -CH2-CH(-CH3)-C(=O)-O-(CH2)2N(-CH3)SO2-H

[0103] The modified polymer of the present invention is obtained by reacting (a) a fluorine-containing polymer with monomers represented by the above general formula (b) and general formula (c) in an organic solvent in the presence of a radical polymerization initiator.

[0104] The temperature of the above reaction is particularly preferably 60°C or higher, more preferably 70°C or higher, even more preferably 80°C or higher, and is preferably 150°C or lower, more preferably 140°C or lower, even more preferably 135°C or lower.

[0105] In the above reaction, the amount of monomer (b) is preferably 1 to 30 parts by mass, more preferably 1 to 20 parts by mass, and further preferably 2 to 10 parts by mass, based on 100 parts by mass of the fluorine-containing polymer (a).

[0106] In the above reaction, the amount of the monomer (c) is preferably 1 to 30 parts by mass, more preferably 1 to 20 parts by mass, and further preferably 2 to 10 parts by mass, based on 100 parts by mass of the fluorine-containing polymer (a).

[0107] In the above reaction, the fluorine-containing polymer can react with monomer (b) and monomer (c) simultaneously, or the fluorine-containing polymer can react with monomer (b) and then further react with monomer (c).Preferably, the fluorine-containing polymer reacts with monomer (b) and monomer (c) simultaneously.In the present invention, the side chain is preferably formed by copolymerization of monomer (b) and monomer (c).

[0108] Examples of organic solvents used in the above reaction include esters such as methyl acetate, ethyl acetate, propyl acetate, n-butyl acetate, and tert-butyl acetate; ketones such as acetone, methyl ethyl ketone, and cyclohexanone; aliphatic hydrocarbons such as hexane, cyclohexane, octane, nonane, decane, undecane, dodecane, and mineral essential oil; aromatic hydrocarbons such as benzene, toluene, xylene, naphthalene, and solvent naphtha; alcohols such as methanol, ethanol, tert-butanol, isopropanol, and ethylene glycol monoalkyl ether; cyclic ethers such as tetrahydrofuran, tetrahydropyran, and dioxane; dimethyl sulfoxide, and the like, or mixtures thereof.

[0109] Examples of the polymerization initiator used in the above reaction include persulfates such as ammonium persulfate and potassium persulfate (which may be used in combination with reducing agents such as sodium bisulfite, sodium metabisulfite, cobalt naphthenate, and dimethylaniline, if necessary); redox initiators composed of an oxidizing agent (e.g., ammonium peroxide, potassium peroxide, etc.), a reducing agent (e.g., sodium sulfite, etc.) and a transition metal salt (e.g., iron sulfate, etc.); diacyl peroxides such as acetyl peroxide and benzoyl peroxide (BPO); dialkoxycarbonyl peroxides such as isopropoxycarbonyl peroxide and tert-butoxycarbonyl peroxide; and ketone peroxides such as methyl ethyl ketone peroxide and cyclohexanone peroxide. hydroperoxides such as hydrogen peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, dialkyl peroxides such as di-tert-butyl peroxide and dicumyl peroxide; alkyl peroxide esters such as tert-butyl peroxyacetate and tert-butyl peroxypivalate; and azo compounds such as 2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2-methylvaleronitrile), 2,2'-azobis(2-cyclopropylpropionitrile), 2,2'-azobisisobutyrate dimethyl, 2,2'-azobis[2-(hydroxymethyl)propionitrile], and 4,4'-azobis(4-cyanopentenoic acid).

[0110] The amount of the radical polymerization initiator is preferably 0.01 to 0.5 parts by mass, more preferably 0.05 parts by mass or more, even more preferably 0.1 parts by mass or more, and more preferably 0.3 parts by mass or less, and even more preferably 0.2 parts by mass or less, relative to the total amount of monomers.

[0111] The above reaction is preferably further carried out in the presence of a chain transfer agent. Examples of the chain transfer agent include thiol group-containing compounds such as dodecyl mercaptan, lauryl mercaptan, thioglycol, and thioglycerol (particularly alkyl mercaptans (e.g., having 1 to 30 carbon atoms)), and inorganic salts such as sodium hypophosphite and sodium hydrogen sulfite. The amount of the chain transfer agent is in the range of 0.1 to 50 parts by mass, for example, 2 to 20 parts by mass, per 100 parts by mass of the total amount of monomers.

[0112] The above reaction is preferably carried out by stirring a mixture containing the fluorine-containing polymer, monomer (b) and monomer (c), an organic solvent, and a radical polymerization initiator.

[0113] A specific method for obtaining the modified polymer of the present invention is, for example, the following method: A fluorine-containing polymer and an organic solvent are added to a reaction vessel, the temperature is raised to 80 to 90°C, and stirring is performed as necessary, and then the above-mentioned monomers (b) and (c) are added, a chain transfer agent and a radical polymerization initiator are added, and then stirring is performed.

[0114] The modified polymer of the present invention has a fluorine-containing polymer main chain and a side chain having a specific structure, and thus can impart excellent antifouling properties in addition to the properties of the fluorine-containing polymer, such as weather resistance, etc. In particular, when the modified polymer is used in a paint, the side chain based on monomer (c) makes it easier for the main chain made of the fluorine-containing polymer (a) to bond with the side chain based on monomer (b), improving the affinity of the system, and as a result, the paint containing the modified polymer of the present invention has long-lasting antifouling properties.

[0115] The content of the component (A) paint resin in the paint I of the present invention is 20 to 40 mass %. From the viewpoint of exerting general performance as a coating film, it is preferably 22 mass % or more, more preferably 25 mass % or more, and even more preferably 30 mass %. Also, from the viewpoint of exerting general performance as a coating film, the content of the component (A) paint resin is preferably 40 mass % or less, more preferably 38 mass % or less. <Ingredient (B)>

[0116] From the viewpoint of achieving the sustained anti-icing effect of the present invention, the component (B) porous filler of the present invention is preferably a porous filler having a porosity of 30% or more. The porosity of the porous filler is preferably 40% or more, more preferably 50% or more, and particularly preferably 55% or more. In addition, from the viewpoint of exerting general performance as a coating film, the porosity of the porous filler is preferably 500% or less, more preferably 400% or less, even more preferably 350% or less, and particularly preferably 300% or less.

[0117] From the viewpoint of achieving a sustained anti-icing effect of the present invention, the material of the porous filler is preferably one or more selected from silica, graphite, diatomaceous earth, mica powder, kaolin, calcium carbonate, titanium dioxide, zinc oxide, quartz powder, and barium sulfate. Among these, from the viewpoint of achieving a good and sustained anti-icing effect, silica, kaolin, and calcium carbonate are preferred, and silica is more preferred.

[0118] The content of the porous filler (B) in the paint I of the present invention is 10 to 30% by mass. From the viewpoint of achieving a sustained anti-icing effect of the present invention, the content is preferably 11% by mass or more, more preferably 15% by mass or more, and even more preferably 18% by mass or more, and from the viewpoint of exerting general performance as a coating film, the content of the porous filler is preferably 30% by mass or less, more preferably 28% by mass or less, and even more preferably 27% by mass or less. <Ingredient (C)>

[0119] The component (C) of the present invention is a hydrophobic auxiliary, and is not particularly limited as long as it is a hydrophobic auxiliary that has been conventionally used in the coating field.The hydrophobic auxiliary of component (C) can be selected from one or more of (meth)acrylate, fluorine-containing (meth)acrylate, silicon-containing (meth)acrylate, dimethyl silicone oil, hydroxy silicone oil, amino silicone oil, perfluoroalkane, and perfluoropolyether, among which silicon-containing (meth)acrylate, dimethyl silicone oil, hydroxy silicone oil, and amino silicone oil are preferred, and dimethyl silicone oil and hydroxy silicone oil are more preferred.

[0120] Examples of the (meth)acrylate include methyl acrylate, ethyl acrylate, methyl 2-methacrylate, and ethyl 2-methacrylate.

[0121] Examples of the fluorine-containing (meth)acrylate include a fluorine-containing (meth)acrylate homopolymer, a fluorine-containing (meth)acrylate random copolymer, a fluorine-containing (meth)acrylate segment copolymer, a fluorine-containing (meth)acrylate core-shell polymer, etc. From the viewpoint of hydrophobicity, the fluorine content in the fluorine-containing (meth)acrylate is preferably 20% or more, more preferably 25% or more, and even more preferably 30% or more.

[0122] Examples of silicon-containing (meth)acrylates include (meth)acrylated silane coupling agents (containing a (meth)acryloyloxy group at one end and a silicone group having another active functional group at the other end), non-bonded silicon-containing mono(meth)acrylates, poly(meth)acrylate silanes or siloxanes, fluorine-containing (meth)acrylate group siloxanes, linear terminal (meth)acryloyloxy polysiloxanes, poly(meth)acryloyloxy polysiloxanes, (meth)acrylated cyclic polysiloxanes, etc. From the viewpoint of hydrophobicity, the silicon content in the silicon-containing (meth)acrylate is preferably 30% or more, more preferably 33% or more, and even more preferably 35% or more.

[0123] Dimethylsilicone oil has a molecular main chain composed of silicon and oxygen atoms, and the side chain connected to the silicon is a methyl group. In the present invention, the weight average molecular weight of the dimethylsilicone oil used as the component (C) hydrophobic auxiliary is 2000 to 50,000, preferably 3,000 to 50,000, and more preferably 4,000 to 50,000.

[0124] The hydroxysilicone oil used in the present invention is a dimethylhydroxysilicone oil, the structural formula of which is HO[(CH3)2SiO]nH, and which is a linear polymer with a main chain of repeating silicon-oxygen bonds, methyl groups as side chains, and hydroxyl groups at the ends. In the present invention, the weight average molecular weight of the hydroxysilicone oil used as component (C) hydrophobic auxiliary is 2000 to 50,000, preferably 3000 to 50,000, more preferably 4,000 to 50,000.

[0125] The aminosilicone oil used in the present invention is obtained, for example, by hydrolyzing an aminoalkylsilane obtained by reacting cyanopropylmethyldichlorosilane (or alkoxysilane) or chloropropylmethyldichlorosilane (or alkoxysilane) with diethylamine, and then copolymerizing the hydrosilane with cyclotetrasiloxane. The weight average molecular weight of the aminosilicone oil used as the hydrophobic auxiliary (component (C)) in the present invention is 2000 to 50,000, preferably 3,000 to 50,000, more preferably 4,000 to 50,000.

[0126] The perfluoroalkane used in the present invention refers to a compound formed by replacing all hydrogen atoms on an alkane molecular chain with fluorine atoms. Examples of perfluoroalkane include perfluorobutane, perfluorooctane, perfluorohexane, and perfluoromethylcyclohexane.

[0127] The main chain of the perfluoropolyether used in the present invention is composed of an ether chain such as -CF2-O-CF2-. The weight average molecular weight of the perfluoropolyether used in the present invention is 2000 to 50,000, preferably 3,000 to 50,000, and more preferably 4,000 to 50,000.

[0128] The content of the hydrophobic auxiliary agent (C) in the paint I of the present invention is 2 to 20 mass %. From the viewpoint of achieving the sustained anti-icing effect of the present invention, it is preferably 2.5 mass % or more, more preferably 3 mass % or more, and even more preferably 5 mass % or more. From the viewpoint of hydrophobicity, the content of the hydrophobic auxiliary agent (C) in the paint I of the present invention is preferably 20 mass % or less, more preferably 18 mass % or less, and even more preferably 15 mass % or less. <Ingredient (D)>

[0129] Component (D) of the present invention is a wax having a melting point of 60 to 160° C. Examples of component (D) of the present invention include paraffin wax, polyoxyethylene wax, polyethylene wax, polypropylene wax, polyamide wax, and polytetrafluoroethylene wax. Among them, from the viewpoint of aging resistance, polyoxyethylene wax, polyethylene wax, polypropylene wax, polyamide wax, and polytetrafluoroethylene wax are preferred, and polyoxyethylene wax, polyethylene wax, polypropylene wax, and polytetrafluoroethylene wax are more preferred.

[0130] From the viewpoint of aging resistance, component (D) has a melting point of 60°C or higher, preferably 65°C or higher, and more preferably 70°C or higher, and from the viewpoint of fluidity, the melting point is preferably 160°C or lower, more preferably 150°C or lower, and even more preferably 140°C or lower.

[0131] The content of the wax as component (D) in the paint I of the present invention is 1 to 10 mass %, and from the viewpoint of achieving a sustained anti-icing effect of the present invention, it is preferably 1.2 mass % or more, more preferably 1.5 mass % or more, and from the viewpoint of the evenness of the coating film, the content of the wax as component (D) of the present invention is preferably 10 mass % or less, more preferably 9.7 mass % or less, and even more preferably 8.50 mass % or less. <Ingredient (E)>

[0132] In the present invention, component (E) is an organic solvent, and is not particularly limited as long as it is an organic solvent that has been conventionally used in the field of paints. Examples of the organic solvent of component (E) include esters such as ethyl acetate, n-butyl acetate, tert-butyl acetate, isopropyl acetate, isobutyl acetate, cellosolve acetate, and propylene glycol methyl ether acetate; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; cyclic ethers such as tetrahydrofuran and dioxane; amides such as N,N-dimethylformamide and N,N-dimethylacetamide; aromatic hydrocarbons such as toluene and xylene; alcohols such as propylene glycol methyl ether; hydrocarbons such as hexane and heptane, and mixed solvents thereof. In addition, examples of the organic solvent include the third organic solvent of the Industrial Safety and Health Act, which is called a weak solvent, and solvents equivalent thereto. The organic solvent of component (E) is preferably acetone, n-butyl acetate (BAC), xylene, propylene glycol methyl ether acetate (PMA), cyclohexanone, methyl amyl ketone (MAK), methyl ethyl ketone (MEK), dibasic acid ester mixtures (DBE), and combinations of solvents formed from two or more of these.

[0133] The content ratio of each component in the solvent combination can be adjusted according to the actual situation. <Other ingredients>

[0134] The paint I of the present invention may contain other components in addition to the above components, and the other components include additives such as leveling agents, defoamers, pigments and dyes, dispersants, preservatives, etc., which are conventionally used in the paint field. The types and contents of these additives in the paint of the present invention can be selected and adjusted as necessary.

[0135] The coating material I of the present invention may further contain a curing agent g1. The type and amount of the curing agent g1 can be selected and determined according to the type and content of the component (A) coating material resin. The types of the curing agent g1 are classified into HDI type, XDI type, IPDI type, and MDI type. In general, the curing agent g1 is stored separately from the coating material I, and the curing agent g1 is added to the coating material I 10 minutes to 2 hours before the coating material I is applied. <Paint I>

[0136] The coating material of the present invention comprises the above-mentioned components (A) to (E): Component (A) Paint resin 20~40% by mass Component (B) Porous filler 10 to 30% by mass Component (C) Hydrophobic auxiliary 2 to 20% by mass Component (D) Wax having a melting point of 60 to 160°C: 1 to 10% by mass Component (E) Organic solvent Balance Contains:

[0137] On the one hand, the paint I of the present invention absorbs and slowly releases the hydrophobic auxiliary (C) through the adsorption and sustained release properties of the porous filler (B), thereby allowing the hydrophobic auxiliary (C) to continuously exert its function, thereby achieving a sustained and efficient anti-icing effect. On the other hand, the wax having a melting point of 60 to 160°C (D) contained in the paint I of the present invention is a component that provides an anti-icing effect, and when a coating film prepared with the paint I of the present invention is exposed to the atmosphere for a long period of time, the wax having a melting point of 60 to 160°C (D) gradually migrates (in the present invention, "migration" mainly refers to floating up) to the surface of the coating film, thereby achieving a sustained and efficient anti-icing effect.

[0138] In paint I of the present invention, from the viewpoint of effectively exerting the synergistic effect of components (B) and (C) to achieve a sustained and efficient anti-icing effect, the mass ratio (B) / (C) of the content of component (B) to the content of component (C) is set to 0.5 or more, preferably 0.9 or more, more preferably 1.1 or more, even more preferably 3.0 or more, and is preferably set to 10 or less, more preferably 9.4 or less, even more preferably 8.6 or less, particularly preferably 6.5 or less. In the present invention, the mass ratio (B) / (C) is 0.9 to 9.4, preferably 1.1 to 8.6, more preferably 3.0 to 6.5.

[0139] In paint I of the present invention, from the viewpoint of effectively exerting the synergistic effect of components (B), (C) and (D) to achieve a sustained and efficient anti-icing effect, the mass ratio of the total amount of the components (B) and (C) to the content of the component (D), [(B)+(C)] / (D), is set to 2 or more, preferably 2.4 or more, more preferably 5 or more, and even more preferably 7 or more, and is preferably set to 24 or less, more preferably 2.6 or less, and even more preferably 20 or less. In the present invention, the mass ratio [(B)+(C)] / (D) is 2.4 to 23.6, preferably 2.6 to 23.6, and more preferably 7 to 20. <Preparation of Paint I>

[0140] The paint I of the present invention can be prepared by a conventional method, for example, the following method can be used. First, the above-mentioned component (A) paint I resin, component (B) porous filler, a part of the component (E) organic solvent, and a dispersant used as needed are charged into a sanding machine containing glass beads and ground for 1 to 3 hours, and then the slurry obtained by grinding is added to a stirring tank, and further the component (C) hydrophobic auxiliary, component (D) wax, the remainder of the component (E) organic solvent, and a leveling agent, defoamer, etc. added as needed are added to the stirring tank, and the mixture is stirred at a rotation speed of 600 to 2000 r / min for 10 to 120 minutes, and filtered to prepare the paint I of the present invention. <Preparation of Coating I>

[0141] The coating material I of the present invention can be applied by a conventional method, for example, an appropriate amount of a curing agent is further added to the prepared coating material I, and the mixture is uniformly stirred and then applied by roll coating, spray coating, curtain coating, etc. When the coating material I of the present invention is applied and the organic solvent is volatilized, a coating film I is formed. The coating film I is cured at 5°C to 300°C to become a coating film I that has anti-icing properties.

[0142] The anti-icing effect of the coating film I of the present invention can be evaluated by measuring the contact angle with water. After the coating film I of the present invention is prepared, the initial contact angle with water of the coating film I is 95° to 110°. After 3000 hours of ultraviolet aging by exposure to artificial radiation (in the present specification, "after ultraviolet aging by exposure to artificial radiation" is sometimes simply referred to as "QUVB3000h"), the contact angle with water of the coating film I is maintained or increases to 95° to 135°.

[0143] For the coating film I of the present invention, the initial contact angle with water, the contact angle with water after 1000 hours of ultraviolet ray aging (QUVB) under artificial radiation exposure, the contact angle with water after 2000 hours of ultraviolet ray aging (QUVB) under artificial radiation exposure, and the contact angle with water after 3000 hours of ultraviolet ray aging (QUVB) under artificial radiation exposure were measured according to GB / T30693-2014. Specifically, the coating material I was applied to a sample plate for measurement (size: length 15 cm x width 7 cm) at 0.02 g / cm2 and cured at a temperature of 25°C for 7 days to produce a sample plate for measurement (size: length 15 cm x width 7 cm). First, a sample plate of QUVB1000h, QUVB2000h, or QUVB3000h was placed on the platform of the water contact angle meter and fixed, and then 2 μL of water droplets were measured on the plate. Six data points were measured per plate, and the average values ​​were recorded in the table below as results.

[0144] The present invention also provides a modified polymer, which is the above modified polymer (A').

[0145] The present invention also provides a coating material II comprising the above modified polymer (A'), a curing agent g2, and an organic solvent E2. The content of the modified polymer (A') in the coating material II is 60%. The contents of the curing agent g2 and the organic solvent E2 in the coating material II may be appropriately set with reference to the conventional techniques in the coating material field.

[0146] As the organic solvent E2, the same ones as the above component (E) can be used.

[0147] The curing agent g2 can be the same as the curing agent g1. On the other hand, considering that the coating material II contains a specific modified polymer (A'), the curing agent g2 is preferably a compound that reacts with the curing functional group of the fluorine-containing polymer containing a curing functional group to cause crosslinking, and for example, isocyanates, amino resins, acid anhydrides, polyepoxy compounds, isocyanate group-containing silane compounds, etc. are generally used. Among them, isocyanates are preferred.

[0148] The paint II of the present invention may further contain additives that are commonly used in the paint field.Examples of the additives include curing accelerators, pigments, dispersants, flow improvers, leveling agents, defoamers, gelling inhibitors, UV absorbers, antioxidants, hydrophilic agents, matting agents, adhesion improvers, flame retardants, etc.The content of these additives may be appropriately specified according to the prior art as necessary. <Preparation of Paint II>

[0149] The paint II of the present invention can be prepared by a conventional method. For example, the modified polymer, the curing agent, the organic solvent E2, and additives added as necessary are added in order in a stirring tank, stirred at a rotation speed of 600 to 2000 rpm for 10 to 120 minutes, and then filtered to prepare the paint. <Preparation of Coating II>

[0150] The present invention also provides a coating film II obtained by applying the coating material II of the present invention. The coating material II of the present invention is applied by a conventional method to obtain the coating film II. For example, after the coating material II is prepared as described above, it is applied by roll coating, spray coating, curtain coating, or the like. The coating material II of the present invention is applied, and after the organic solvent has evaporated, a coating film II is formed, and the coating film II can be dried and cured at 5°C to 300°C, and is usually dried and cured at 100 to 200°C for 30 seconds to 3 days.

[0151] The coating film II has excellent weather resistance and antifouling properties due to the inclusion of the modified polymer of the present invention. The coating film II is preferably a cured coating film.

[0152] [Examples 1-1 to 1-12, Examples 2-1 to 2-9, and Comparative Examples 1 to 9]

[0153] Paint I of the examples and comparative examples was prepared with the compositions shown in the following Tables 1 to 3. For Paint I of the examples and comparative examples, a hardener was prepared with the compositions shown in the following tables, stirred at a rotation speed of 800 r / min for 30 minutes, and a measurement sample plate was produced by roll coating and spray coating.

[0154] The values ​​shown in Tables 1 to 3 are all amounts shown as active ingredients. The amounts of curing agent used (mass %) shown in Tables 1 to 3 are amounts when the amount of paint used is 100 mass %.

[0155] Detailed information about each component used in the examples and comparative examples is as follows: DKF-025: Hydroxyacrylic resin as component (A), DKF-025, manufactured by Dongsheng Chemical Co., Ltd., China. Polymer (1): 1840.0g of butyl acetate, 620.0g of vinyl neononanoate, and 160.0g of 4-hydroxybutyl vinyl ether (HBVE) were added to a 6000ml stainless steel autoclave, and the pressure was reduced and the mixture was replaced with nitrogen gas. 478.0g of tetrafluoroethylene (TFE) was then added. The temperature of the reaction vessel was raised to 60°C, and a specified amount of peroxide initiator was added. The reaction was continued for 5 hours at 60°C to obtain polymer (1). The hydroxyl value of the obtained polymer was 63.0mgKOH / g. Polymer (2): 200g of polymer (1) (main chain reactant solution) and 20g of butyl acetate were added to a 1L reaction vessel, the temperature was raised to 90°C and stirred for 30 minutes. Then, 6.5g of tridecafluorooctyl acrylate (side chain reactant), 1.3g of 4-hydroxybutyl acrylate, 1.3g of glycidyl methacrylate, and a mixed solution of 0.1365g of chain transfer agent dodecyl mercaptan, 0.1183g of dibenzoyl peroxide initiator, and 15g of butyl acrylate were added dropwise over 1 hour. Then, the mixture was stirred at 90°C for 2 hours to synthesize polymer (2). Both the main chain and side chain of polymer (2) contain fluorine. Polymer (3): 200g of the main chain reactant solution of polymer (1) and 20g of butyl acetate were added to a 1L reaction vessel, the temperature was raised to 90°C and stirred for 30 minutes. Then, a mixed solution of 3.9g of the side chain reactant polydimethylsiloxane acrylate, 0.78g of 4-hydroxybutyl acrylate, 0.05148g of the chain transfer agent dodecyl mercaptan, 0.06084g of the initiator dibenzoyl peroxide, and 15g of butyl acetate was added dropwise over 1 hour. Then, the mixture was stirred at 90°C for 2 hours to synthesize polymer (3). The main chain of polymer (3) contains fluorine and the side chain contains silicon. Polymer (3) is the component corresponding to modified polymer (A'). Silica: porosity 200-300%, TS-100, manufactured by Evonik Degussa. Kaolin: porosity 50-100%, HY-T-80, manufactured by Shanxi Hengyuan Co., Ltd., China. Calcium carbonate: porosity 30-50%, Z-2000, manufactured by Nanjing Chendong New Materials Co., Ltd., China. Silicone oil 14K: Dimethicone, weight average molecular weight 13700, STARSILDM350, manufactured by China Xinghuo Silicone Co., Ltd. Silicone oil 50K: Dimethyl silicone oil, average molecular weight 50,000, manufactured by China Xinghuo Silicone Co., Ltd. Perfluoroalkane 2K: Perfluoroalkane, weight average molecular weight 2000, DEMNUMS20, manufactured by Daikin Fluorochemicals (China) Co., Ltd. Polyethylene wax: melting point 100-120℃, CERAFLOUR991, manufactured by BYK. Paraffin wax: melting point 60-70℃, TP-66, manufactured by Tianshi Wax Powder Co., Ltd., China. Polypropylene wax: melting point 160℃, BYK-970, manufactured by BYK. Hardener: HDI terpolymer, N3390, manufactured by Covestro. Leveling agent: BYK358N, manufactured by BYK. Defoamer: BYK052N, manufactured by BYK.

[0156] [Table 1]

[0157] [Table 2]

[0158] [Table 3]

[0159] As can be seen from Tables 1 and 2, the paints of Examples 1-1 to 1-12 and Examples 2-1 to 2-10 contain specific components (B), (C) and (D) in specific amounts, so that the coating film has a high initial contact angle with water of 95 to 110°, and after 3,000 hours of ultraviolet aging due to exposure to artificial radiation, the contact angle with water is maintained or increases to a relatively high value of 95 to 135°.

[0160] On the other hand, the following was found from Table 3.

[0161] The coating films of Comparative Examples 1 and 2, which contained only component (A), had contact angles with water initially and after 3,000 hours of ultraviolet aging through exposure to artificial radiation that were not in the range of 95 to 110°, indicating that good anti-icing effects were not obtained.

[0162] The coating films of Comparative Examples 3 and 4, which contained only component (A), Comparative Example 5, which contained only components (A) and (B), Comparative Example 6, which contained only components (A) and (C), and Comparative Example 7, which contained only components (A) and (D), had high initial contact angles with water of 95 to 110°, but after 3,000 hours of ultraviolet aging from exposure to artificial radiation, none of the contact angles with water were 95 to 110°, and a significant decrease was observed, indicating that the durability of the anti-icing effect was poor.

[0163] The coating films of Comparative Example 8, which did not contain component (D), and Comparative Example 9, which did not contain component (C), had high initial contact angles with water of 95 to 110°, but after 3,000 hours of ultraviolet aging due to exposure to artificial radiation, the contact angles with water did not reach 95 to 110° in any case, and a significant decrease was observed, indicating that the durability of the anti-icing effect was poor. [Example 3 and Comparative Example 1]

[0164] Paint II of Example 3 and Comparative Example was prepared with the composition shown in Table 4. Using Paint II, a sample plate for measurement was produced by spray coating.

[0165] Detailed information on each component used in Example 3 and Reference 1 is as follows: Polymer (1): Same as Polymer (1) in Tables 1 to 3 above Polymer (3): Same as polymer (3) in Tables 1 to 3 above Hardener: HDI terpolymer, N3390, manufactured by Covestro. Leveling agent: BYK358N, manufactured by BYK. Defoamer: BYK052N, manufactured by BYK. <Anti-stain performance test method>

[0166] The antifouling performance was evaluated with reference to GB / T9780-2013 "Test method for stain resistance of architectural coatings." The specific steps are as follows: (1) Preparation of coating film: A coating film was prepared using a cement board as the base material by a coating preparation method, and the film was left at 25°C for 7 days to harden. (2) Preparation of contamination source suspension: An appropriate amount of the experimental ash standard sample was weighed out, mixed with water in a 1:1 ratio, and stirred uniformly to prepare a suspension. (3) Measurement of initial reflectance coefficient: After curing, the initial reflectance coefficient of the coating film was measured at three points, the top, middle, and bottom of the sample plate, and the average value A was taken. (4) Brushing: Using a soft brush, the contamination suspension was applied uniformly to the surface of the sample plate in the horizontal and then vertical directions. The amount of contamination suspension applied was (0.7±0.1) g per sample plate. (5) Quick drying: The sample plate was placed in an oven at 60°C ± 2 for 30 minutes, then removed and left for 2 hours under standard experimental conditions. (6) Measurement of reflectance after contamination: The sample plate was placed on the sample plate stand of the cleaning device, and the valve of the cleaning device filled with 15 L of water was opened to the maximum to rinse the coated sample plate. The coated sample plate was moved continuously during cleaning so that the water flow could rinse all parts evenly. After rinsing, the sample plate was left for 24 hours before measurement. (7) Measurement of reflection coefficient after contamination: The reflection coefficient of the coating film was measured at three points, top, middle, and bottom, and the average value B was taken. (8) Calculation of stain resistance: X = |AB| / A x 100%

[0167] The prepared coating film was measured according to the above-mentioned <Anti-soiling performance test method> at the initial preparation stage, after 3000 hours of UV aging (QUVB) by artificial radiation exposure, and after 5 months of outdoor exposure. The smaller the X value obtained by the measurement, the better the anti-soiling performance.

[0168] [Table 4]

[0169] The coatings obtained in the examples showed good stain resistance, with a stain resistance of 5.3% after 2000 hours of QUVB aging and 2.8% after 5 months of outdoor exposure.

Claims

1. The following components (A) to (E): Component (A) Paint resin 20-40% by mass Component (B) Porous filler 10-30% by mass Component (C) Hydrophobic auxiliary 2 to 20% by mass Component (D) Wax with a melting point of 60 to 160°C: 1 to 10% by mass Component (E) Organic solvent Balance A paint comprising:

2. 2. The coating material according to claim 1, wherein the component (A) is at least one selected from the group consisting of hydroxyacrylic resins, polyester resins, silicone resins, fluorocarbon resins, and fluorosilicone resins.

3. 3. The coating material according to claim 2, characterized in that the component (A) is a fluorosilicone resin.

4. The component (A) is (a) a main chain composed of a fluorine-containing polymer; The coating material according to claim 1, which is a modified polymer having side chains based on monomers represented by general formulas (b) and (c). CH2=C(-R1)-C(=O)-O-Si(-CH3)2-[O-Si(-CH3)2]nO-Si(-CH3)2-R2 (b) (In the formula, R1 is a hydrogen atom or a methyl group, R2 is a hydrogen atom or a methyl group, and n is 3 to 200.) CH2=C(-R3)-C(=O)-XY (c) (In the formula, R3 is a hydrogen atom or a methyl group, X is O or N, and Y is a group selected from a linear alkyl group, a cyclic alkyl group, a hydroxyl group, an amino group, a carboxyl group, an amide group, and an epoxy group.)

5. 2. The coating material according to claim 1, wherein the component (B) is a porous filler having a porosity of 30% or more.

6. The paint according to any one of claims 1 to 4, characterized in that the component (B) is one or more selected from the group consisting of silica, graphite, diatomaceous earth, mica powder, kaolin, calcium carbonate, titanium dioxide, zinc oxide, quartz powder, and barium sulfate.

7. 7. The coating material according to claim 6, wherein the component (B) is one or more selected from the group consisting of silica, kaolin, and calcium carbonate.

8. The paint according to any one of claims 1 to 5, characterized in that the component (C) is one or more selected from the group consisting of (meth)acrylates, fluorine-containing (meth)acrylates, silicon-containing (meth)acrylates, dimethylsilicone oils, hydroxysilicone oils, aminosilicone oils, perfluoroalkanes, and perfluoropolyethers.

9. The paint according to claim 8, characterized in that the weight average molecular weight of the component (C) is 2,000 to 50,000.

10. The paint according to any one of claims 1 to 5, characterized in that the mass ratio (B) / (C) of the content of component (B) to the content of component (C) is 0.9 to 9.

4.

11. The paint according to claim 10, characterized in that the mass ratio (B) / (C) of the content of component (B) to the content of component (C) is 1.1 to 8.

6.

12. The paint according to claim 10, characterized in that the mass ratio (B) / (C) of the content of component (B) to the content of component (C) is 3.0 to 6.

5.

13. The paint according to any one of claims 1 to 5, characterized in that the mass ratio [(B) + (C)] / (D) of the sum of the content of component (B) and the content of component (C) to the content of component (D) is 2.4 to 23.

6.

14. The paint according to claim 13, characterized in that the mass ratio [(B) + (C)] / (D) of the sum of the content of component (B) and the content of component (C) to the content of component (D) is 7 to 20.

15. The paint according to any one of claims 1 to 5, characterized in that the component (D) is one or more waxes selected from paraffin wax, polyoxyethylene wax, polyethylene wax, polypropylene wax, polyamide wax, and polytetrafluoroethylene wax.

16. A coating film obtained by applying the coating material according to any one of claims 1 to 15.

17. an initial water contact angle of between 95° and 110°; and / or The coating film according to claim 16, characterized in that the contact angle with water after 3000 hours of ultraviolet aging by exposure to artificial radiation is 95° to 135°.

18. Use of the paint according to any one of claims 1 to 15 for anti-icing.

19. 19. Use according to claim 18, characterized in that the coating is used on wind turbine blades, bridge lock cables, power systems, heat exchanger fins.

20. (a) a main chain composed of a fluorine-containing polymer; and side chains based on monomers represented by general formulas (b) and (c). CH2=C(-R1)-C(=O)-O-Si(-CH3)2-[O-Si(-CH3)2]nO-Si(-CH3)2-R2(b) (In the formula, R1 is a hydrogen atom or a methyl group, R2 is a hydrogen atom or a methyl group, and n is 3 to 200.) CH2=C(-R3)-C(=O)-XY(c) (In the formula, R3 is a hydrogen atom or a methyl group, X is O or N, and Y is a group selected from a linear alkyl group, a cyclic alkyl group, a hydroxyl group, an amino group, a carboxyl group, an amide group, and an epoxy group.)

21. The modified polymer according to claim 20, wherein the (a) fluorine-containing polymer contains polymerized units based on tetrafluoroethylene or chlorotrifluoroethylene.

22. 22. A coating material comprising the modified polymer according to claim 20 or 21, a curing agent and an organic solvent.

23. A coating film obtained by applying the coating material according to claim 22.

24. 23. Use of the paint according to claim 22 in antifouling.

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