Copolymer, liquid-repellent agent, liquid-repellent composition, cured resin, and article

Abstract

To provide a liquid-repellent agent having high heat resistance.SOLUTION: Provided is a copolymer of monomers comprising: (A) a (meth)acrylate monomer containing a perfluoroether moiety and an amide bond; (B) a (meth)acrylate monomer containing an epoxy group; and (C) a (meth)acrylate monomer containing a hydroxyl group.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a copolymer, a liquid repellent agent containing the copolymer, a liquid repellent composition containing the liquid repellent agent, a cured resin which is a cured product of the liquid repellent composition, and an article containing the liquid repellent cured resin. [Background technology]

[0002] In order to manufacture devices such as display pixels, wiring, color filters, and biochips using printing techniques such as inkjet printing, it is necessary to pattern the substrate in advance into liquid-repellent and liquid-philic regions on a micrometer scale using photolithography. To obtain liquid-repellent regions, for example, liquid-repellent agents are added to UV-curable resin compositions, color resists, etc.

[0003] However, when a high-performance liquid repellent agent is added to a curable resin composition, a color resist, or the like, there are problems such as the color resist becoming cloudy and repelling occurring on the resist surface.

[0004] When the fluorine-containing oligomer disclosed in Patent Document 1 is added to a UV-curable resin composition, a color resist, or the like, the above-mentioned turbidity and cissing do not occur, but the liquid repellency is insufficient.

[0005] Under such circumstances, the present inventors have developed a liquid repellent agent composed of a urethane-based reaction product obtained by reacting a hydroxyl-containing fluorine-based polymer with at least one isocyanate-containing (meth)acrylate-based monomer, the hydroxyl-containing fluorine-based polymer being obtained by copolymerizing the following monomers (A) to (C) (Patent Document 2): (A) at least one (meth)acrylate-based monomer containing a perfluoroether moiety; (B) at least one hydroxyl-containing (meth)acrylate-based monomer; (C) at least one (meth)acrylate-based monomer. When a composition in which the liquid repellent agent is added to a UV-curable resin or color resist is applied to a substrate or the like and cured, the liquid repellent agent of the present invention reacts with the curing component contained in the UV-curable resin or color resist to give liquid repellency to the cured resin, such as a cured film. However, the liquid repellent agent may not be sufficient in terms of heat resistance, and there is a demand for the development of a liquid repellent agent with higher heat resistance. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Patent No. 5997998 [Patent Document 2] Patent Publication No. 2021-187961 Summary of the Invention [Problem to be solved by the invention]

[0007] An object of the present invention is to provide a liquid repellent agent having high heat resistance. [Means for solving the problem]

[0008] Under such circumstances, the present inventors have conducted intensive research and have found the following (A) to (C): (A) (Meth)acrylate Monomer Containing a Perfluoroether Moiety and an Amide Bond (B) Epoxy group-containing (meth)acrylate monomer (C) Hydroxyl group-containing (meth)acrylate monomer It has been found that the above problems can be solved by using a copolymer of monomers containing the following. The present invention is based on this new finding. Accordingly, the present invention provides the following: Item 1. (A) to (C) below (A) (Meth)acrylate Monomer Containing a Perfluoroether Moiety and an Amide Bond (B) Epoxy group-containing (meth)acrylate monomer (C) Hydroxyl group-containing (meth)acrylate monomer A copolymer of monomers comprising:

[0009] Item 2. The copolymer according to item 1, wherein the (meth)acrylate monomer containing a perfluoroether moiety and an amide bond is represented by the following (A1): [ka] [In the formula, R 1 represents a hydrogen or a methyl group. R 2 represents a divalent saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms (the saturated aliphatic hydrocarbon group may be linear or branched, and may have an ether bond (-O-) or an ester bond (-CO-O- or -O-CO-)). n represents an integer from 0 to 10.

[0010] Item 3. The copolymer according to item 1 or 2, wherein the (meth)acrylate monomer containing a perfluoroether moiety and an amide bond has a molecular weight of 400 to 2,200.

[0011] Item 4. The copolymer according to any one of Items 1 to 3, having a fluorine content of 5 to 40 mass %.

[0012] Item 5. A liquid repellent comprising the copolymer according to any one of items 1 to 4.

[0013] Item 6. The liquid repellent according to item 5, which is dissolved in a solvent.

[0014] Item 7. The liquid repellent according to item 5, which is added to a thermosetting resin.

[0015] Item 8. A liquid-repellent composition comprising a thermosetting resin and the liquid-repellent agent according to item 5.

[0016] Item 9. A liquid-repellent cured resin which is a cured product of the liquid-repellent composition according to item 8.

[0017] Item 10. An article comprising the liquid-repellent cured resin according to item 9. Effect of the Invention

[0018] According to the present invention, it is possible to provide a liquid repellent agent having high heat resistance. In a typical embodiment, it is possible to provide a liquid repellent agent in which the change in liquid repellency (contact angle of the cured coating film) is suppressed even when cured by a high temperature process (200 to 280°C). The liquid repellent agent of the present invention can be combined with a thermosetting resin to obtain a cured product by heat curing, and therefore has the advantage that it can be cured to a deeper part of a thicker resin composition compared to UV curing. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0019] In the present invention, the (meth)acrylate refers to an acrylate or a methacrylate. The present invention relates to the following (A) to (C): (A) (Meth)acrylate Monomer Containing a Perfluoroether Moiety and an Amide Bond (B) Epoxy group-containing (meth)acrylate monomer (C) Hydroxyl group-containing (meth)acrylate monomer The present invention provides a copolymer of a monomer comprising:

[0020] Component (A): A (meth)acrylate monomer containing a perfluoroether moiety and an amide bond. The perfluoroether moiety of the (meth)acrylate monomer having a perfluoroether moiety and an amide bond may be -O-(perfluoroalkyl group), -O-(perfluoroalkylene group), (perfluoroalkylene group)-O-(perfluoroalkyl group), etc.

[0021] Specific examples of perfluoroalkyl groups include -CF3, -CF2CF3, -CF2CF2CF3, -CF(CF3)2, -CF2CF2CF2CF3, and the like. Examples of such linear or branched C1 to C8, preferably C1 to C4 perfluoroalkyl groups include perfluoroalkyl groups having a linear or branched structure.

[0022] Specific examples of the perfluoroalkylene group include linear or branched divalent C2 to C8, preferably C2 to C4 perfluoroalkylene groups such as -CF2-, -CF2CF2-, -CF(CF3)-, -CF2CF2CF2-, -CF2CF(CF3)-, -CF(CF3)CF2-, and -CF2CF2CF2CF3-.

[0023] The (meth)acrylate monomer containing a perfluoroether moiety and an amide bond is preferably represented by the following formula (A1).

[0024] [ka] [In the formula, R 1 represents a hydrogen or a methyl group. R 2 represents a divalent saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms (the saturated aliphatic hydrocarbon group may be linear or branched, and may have an ether bond (-O-) or an ester bond (-CO-O- or -O-CO-)). and n represents an integer from 0 to 10.

[0025] In the above formula (A1), "-C2F4-" represents -CF2-CF2- or -CF(CF3)-, preferably -CF(CF3)-. In the above formula (A1), "-C3F6O-" represents -CF2-CF2-CF2-O-, -CF(CF3)-CF2-O-, or -CF2-CF(CF3)-O-, preferably -CF2-CF(CF3)-O-.

[0026] The integer n is preferably 10 or less, more preferably 7 or less, even more preferably 5 or less, even more preferably 3 or less, and even more preferably 1 or less. The integer n is preferably 1 or more.

[0027] Examples of the divalent saturated aliphatic hydrocarbon group include divalent saturated aliphatic hydrocarbon groups having C1 to C10, preferably C1 to C6, and more preferably C1 to C4, such as -CH2-, -CH2CH2-, -CH(CH3)-, -CH2CH2CH2-, -CH2CH(CH3)-, -CH(CH3)CH2-, and -CH2CH2CH2CH3-.

[0028] In addition, examples of the divalent saturated aliphatic hydrocarbon group having an ether bond include -CH2-O-CH2CH2-, -CH2CH2-O-CH2-, -(CH2CH2-O) l - (l is an integer of 1 to 5). Examples of the divalent saturated aliphatic hydrocarbon group having an ester bond include -CH2CH2-COO-, -CH2CH2-OCO-, -CH2CH2CH2-COO-, -CH2CH2CH2-OCO-, -CH2CH2-COO-CH2-, -CH2CH2-OCO-CH2-, and the like. Examples of the divalent saturated aliphatic hydrocarbon group having an amide bond include -CH2CH2-NHCO-, -CH2CH2-CONH-, -CH2-NHCO-CH2-, -CH2-CONH-CH2-, and the like. The molecular weight of the (meth)acrylate monomer containing a perfluoroether moiety and an amide bond is preferably 400 to 2200, more preferably 400 to 1000, and further preferably 500 to 800.

[0029] The (meth)acrylate monomer containing a perfluoroether moiety and an amide bond may be used alone or in combination of two or more kinds.

[0030] Component (B): Epoxy group-containing (meth)acrylate monomer In the present invention, the epoxy group-containing (meth)acrylate monomer is [ka] In a typical embodiment, the epoxy group-containing (meth)acrylate monomer has, for example, 1 to 2 epoxy groups, preferably 1. In the epoxy group-containing (meth)acrylate monomer, the epoxy group is 7-Oxabicyclo[4.1.0]heptan-3-yl group: [ka] , glycidyl group: [ka] , an oxiranyl group: [ka] etc., with 7-oxabicyclo[4.1.0]heptan-3-yl group etc. being preferred. More specifically, examples of epoxy group-containing (meth)acrylate monomers include (7-oxabicyclo[4.1.0]heptan-3-yl)methyl (meth)acrylate, (meth)acrylate glycidyl, 4-hydroxybutyl (meth)acrylate glycidyl ether, (meth)acrylic acid 9,10-epoxyoctadecanoic anhydride, (meth)acrylic acid=3,4-epoxytricyclo[5.2.1.0]heptan-3-yl ... 2,6 ]decyl, and the like, and (7-oxabicyclo[4.1.0]heptan-3-yl)methyl(meth)acrylate, etc. are preferred. The epoxy group-containing (meth)acrylate monomers may be used alone or in combination of two or more kinds. Commercially available epoxy group-containing (meth)acrylate monomers include Light Ester G (Kyoeisha Chemical Co., Ltd.), 4HBAGE (Mitsubishi Chemical Corporation), and Cyclomer M100 (Daicel Corporation).

[0031] Component (C): Hydroxyl group-containing (meth)acrylate monomer In a typical embodiment, the number of hydroxyl groups in the hydroxyl group-containing (meth)acrylate monomer is 1 or 2, preferably 1. A preferred hydroxyl group-containing (meth)acrylate monomer is represented by the following formula (C1):

[0032] [ka] (In the formula, R 5 represents H or a methyl group. R 6 represents a linear or branched alkylene group. m represents an integer of 1 to 20. These may be used alone or in combination of two or more.

[0033] Examples of linear or branched alkylene groups include C1 to C4 alkylene groups such as -CH2-, -CH2CH2-, -CH(CH3)-, -CH2CH2CH2-, -CH2CH(CH3)-, -CH(CH3)CH2-, and -CH2CH2CH2CH3-. Commercially available hydroxyl group-containing (meth)acrylate monomers include 4-HBA (Osaka Organic Chemical Industry Co., Ltd.), 2-HEMA (Mitsubishi Gas Chemical Company, Inc.), and the Blenmer series (PE-90, PE-200, PE-350, PP-500, PP-800, PP-1000, AE-90U, AE-200, AE-400, AP-200, AP-400, AP-550, AP-800; NOF Corporation).

[0034] Component (D): Other monomers In the present invention, the monomer raw material of the copolymer may further contain monomers (other monomers) other than the above (A) to (C) within the range in which the effects of the present invention can be obtained. Examples of the other monomers include (meth)acrylate monomers other than the above. Examples of the (meth)acrylate monomer include methyl acrylate (MA), ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate (4-HBMA), isobutyl acrylate, s-butyl acrylate, t-butyl acrylate, pentyl acrylate, hexyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, phenyl acrylate, benzyl acrylate, methyl methacrylate (MMA), ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, pentyl methacrylate, hexyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, phenyl methacrylate, and benzyl methacrylate. These may be used alone or in combination of two or more.

[0035] Synthesis of the copolymer of the present invention The copolymer of the present invention can be obtained by copolymerizing raw material monomers including the above-mentioned components (A), (B) and (C). The copolymerization reaction proceeds advantageously by reacting in the presence of a radical initiator at 70 to 90°C for 4 to 12 hours. As the radical initiator, it is preferable to carry out the polymerization in the presence of a radical polymerization initiator. Examples of radical polymerization initiators that can be used in the production method of the present invention include t-butyl hydroperoxide, cumene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, dicumyl peroxide, di-t-butyl peroxide, t-butyl peroxyisobutyrate, t-butyl-α-cumyl peroxide, di-α-cumyl peroxide, α,α'-bis(t-butylperoxy)-p-diisopropylbenzene, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, 2,5-dimethyl-2,5-di(t-butylperoxy)-hexyne-3 acetyl peroxide, succinic acid peroxide, diisobutyryl peroxide, lauroyl peroxide, benzoyl peroxide, t-butyl peroxyacetate, and t-butyl peroxyisobutyrate. , di-isobutyl peroxydicarbonate, t-butyl peroxyisopropyl carbonate, methyl ethyl ketone peroxide, cyclohexanone peroxide, 2,2'-azobisisobutyronitrile, dimethyl = 2,2'-azobisisobutyrate, dimethyl azobisisobutyrate (V-601), 2,2'-azobis (2-methylbutyronitrile), 2,2'-azobis (isobutylamidine) dihydrochloride, 2,2'-azobis [2- (2-imidazolin-2-yl) propane] and its disulfate, 2,2'-azobis (2-methylamidoxime) dihydrochloride and other azo compounds; potassium persulfate, sodium persulfate, ammonium persulfate, potassium persulfate, t-butyl hydroperoxide, benzoyl peroxide, cumene hydroperoxide, and the like. These radical polymerization initiators may be used alone or in combination of two or more.The molecular weight of the copolymerization reaction may be adjusted using a chain transfer agent such as lauryl mercaptan, octyl mercaptan, dodecyl mercaptan, 2-mercaptoethanol, octyl thioglycolate, 3-mercaptopropionic acid, or thioglycerin.

[0036] The proportions of the components (A), (B), and (C) used to obtain the copolymer of the present invention are expressed as follows, with the total of these being 100 mass %: Component (A): preferably 30 to 70 mass%, more preferably 30 to 50 mass%, Component (B): preferably 10 to 40 mass%, more preferably 10 to 30 mass%, Component (C): preferably 20 to 60 mass%, more preferably 30 to 50 mass%, It is.

[0037] The fluorine content of the copolymer of the present invention is preferably 5 to 40% by mass, more preferably 10 to 35% by mass, and further preferably 10 to 25% by mass. From the viewpoint of suppressing the occurrence of cissing on the surface of the cured resin obtained by mixing with a thermosetting resin and curing it, and obtaining high liquid repellency, the fluorine content is preferably in the above range.

[0038] The weight average molecular weight of the copolymer of the present invention is preferably 3000 to 50000, and more preferably 3000 to 10000. The weight average molecular weight can be calculated as a value converted into the molecular weight of standard polystyrene by gel permeation chromatography (GPC).

[0039] Liquid repellent agents, liquid repellent compositions, liquid repellent cured resins, and articles In a preferred embodiment, when a composition in which the liquid repellent agent of the present invention is added to a thermosetting resin is applied to a substrate or the like and cured, liquid repellency can be imparted to the cured resin, such as a cured film obtained by reaction of the curing component contained in the thermosetting resin with the liquid repellent agent of the present invention.

[0040] The liquid repellent of the present invention is preferably a liquid liquid repellent that contains the copolymer of the present invention and further contains a solvent. Solvents include methylene chloride, chloroform, carbon tetrachloride, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane, 1,1,1-trichloroethane, trichloroethylene, perchloroethylene, tetrachlorodifluoroethane, trichlorotrifluoroethane, methyl acetate, ethyl acetate, butyl acetate, amyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, tetrahydrofuran, 1,3-dioxolane, 1,4-dioxane, cyclohexanone, ethyl formate, 2,2,2-trifluoroethanol, 2,2,3,3-hexafluoro-1-propanol, 1,3-difluoro-2-propanol, 1,1,1,3,3,3-hexafluoro-2-methyl-2-propanol, nitroethane, propylene glycol, propylene glycol monomethyl ether, and propylene glycol monomethyl ether acetate (PGME). A), dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol monomethyl ether acetate, dipropylene glycol diacetate, tripropylene glycol, 3-methoxybutyl acetate (MBA), 1,3-butylene glycol diacetate, cyclohexanol acetate, dimethylformamide (DMF), dimethyl sulfoxide, methyl cellosolve, cellosolve acetate, butyl cellosolve, butyl carbitol, carbitol acetate, ethyl lactate, isopropyl alcohol, methanol, ethanol, pentane, hexane, heptane, octane, cyclohexane, benzene, toluene, xylene, anisole, tetralin, cyclohexylbenzene, mesitylene, petroleum ether, tetrahydrofuran, 1,4-dioxane, etc.

[0041] The liquid repellent agent of the present invention can be added to a thermosetting resin to form a liquid repellent composition. The thermosetting resin and the liquid repellent composition are preferably liquid. By curing this liquid repellent composition, liquid repellency can be imparted to the cured resin. The liquid repellent agent of the present invention can be added to a thermosetting resin to impart liquid repellency to the cured product, and is therefore useful as a liquid repellent additive for thermosetting resins.

[0042] The liquid repellent of the present invention maintains its liquid repellency even after heating. The maintenance of the liquid repellency after heating can be evaluated, for example, by mixing the liquid repellent with a cured resin to produce a liquid repellent composition, and measuring the difference in contact angle between a liquid dropped onto a resin (film) obtained by heating and drying the liquid repellent composition, and a contact angle between a liquid dropped onto a cured resin (film) that has been further heated and cured at a high temperature. For example, in the method described in the examples of the present application below, specifically, U-varnish A (polyimide resin, manufactured by UBE Corporation, solid content 20 wt%) diluted with DMF to a solid content concentration of 5% is added with the liquid repellent of the present invention at a solid content of 1% (0.05% in the coating liquid), which is then coated on a 10 cm square glass plate using a spin coater (500 rpm, 10 seconds), heated at 110°C for 3 minutes, and the coating film dried, and the dried coating film further heated at 250°C for 60 minutes are each measured for contact angle when anisole is dropped onto the coating film using DMo-702 (manufactured by Kyowa Interface Science Co., Ltd.). A liquid repellent with a difference of less than 10° is preferred, and a liquid repellent with a difference of less than 5° is more preferred.

[0043] Examples of the thermosetting resin that can be used include polyimide resin, polyamide resin, epoxy resin, urea resin, melamine resin, phenol resin, unsaturated polyester resin, alkyd resin, urethane resin, silicone resin, vinyl ester resin, and fiber reinforced glass (FRP) (e.g., glass fiber reinforced plastic (GFRP), carbon fiber reinforced plastic (CFRP), and aramid fiber reinforced plastic (AFRP)). The thermosetting resin of one preferred embodiment is used for manufacturing color filters, color resists, and the like. The color resist includes a resist (black resist) for manufacturing a black matrix. The thermosetting resin may be a bifunctional or higher curing resin in order to satisfy physical properties such as heat resistance, hot water resistance, and chemical resistance. The thermosetting resin is preferably one that exhibits low molecular weight and amorphousness in order to obtain a low-viscosity liquid-repellent composition.

[0044] The liquid-repellent composition of the present invention preferably contains 1 to 40 mass% of thermosetting resin (solid content) and 0.01 to 0.5 mass% of solid content of the liquid repellent agent, and more preferably contains 1 to 30 mass% of thermosetting resin (solid content) and 0.01 to 0.2 mass% of solid content of the liquid repellent agent, with the total solid content being 100 mass%.

[0045] In a typical embodiment, the liquid-repellent composition of the present invention is heated and cured to obtain a liquid-repellent cured resin. The curing can be performed under the curing conditions of the thermosetting resin. In a preferred embodiment, the liquid-repellent composition of the present invention is applied to a substrate and heated and cured to obtain an article having a cured film as a cured resin. This cured film has a liquid-repellent surface. Examples of the substrate include silicon wafers, synthetic resins, glass, metals, and ceramics. The synthetic resin may be either a thermoplastic resin or a thermosetting resin. Examples of the glass include silicate glass, alkali silicate glass, soda-lime glass, potassium-lime glass, lead glass, barium glass, and borosilicate glass. Examples of the metal include gold, silver, copper, iron, nickel, aluminum, and platinum. Examples of ceramics include oxides (e.g., aluminum oxide, zinc oxide, titanium oxide, silicon oxide, zirconia, barium titanate), nitrides (e.g., silicon nitride, boron nitride), sulfides (e.g., cadmium sulfide), carbides (e.g., silicon carbide), and the like.

[0046] The liquid-repellent composition can be applied to a substrate by, for example, roll coating, gravure coating, microgravure coating, flow coating, bar coating, spray coating, die coating, spin coating, dip coating, or the like, and can be selected in consideration of the type, shape, productivity, controllability of film thickness, and the like of the substrate.

[0047] Hereinafter, specific embodiments of the present invention will be described in detail using examples, but the present invention is not limited to such examples. EXAMPLES

[0048] The present invention will be described in detail below with reference to examples.

[0049] Materials used CAE-600 (Sinochem): methyl 2,3,3,3-tetrafluoro-2-(1,1,2,3,3,3-hexafluoro-2-(perfluoropropoxy)propoxy)propanoate [ka]

[0050] MEA: monoethanolamine [ka]

[0051] Acryloyl chloride [ka]

[0052] Methacryloyl chloride [ka]

[0053] Fluoromonomer C (Sinochem (AC-600)): 2-((2,3,3,3-tetrafluoro-2-(1,1,2,3,3,3-hexafluoro-2-(perfluoropropoxy)propoxy)propanoyl)oxy)ethyl methacrylate [ka]

[0054] Cyclomer M100 (Daicel Corporation): (7-oxabicyclo[4.1.0]heptan-3-yl)methyl methacrylate [ka]

[0055] AE-400 ((NOF Blenmar AE-400)): polyethylene glycol-monoacrylate [ka]

[0056] Synthesis Example 1: Synthesis of Fluorine Monomer A 1. Amidation of CAE-600 with MEA CAE-600 (70g, 0.1373mol) and acetonitrile (70g) were placed in a 200mL eggplant flask containing a stirrer. Next, MEA (8.38g, 0.1373mol) was added and stirred at 50°C for 6 hours. After cooling, the acetonitrile and methanol produced by the reaction were distilled off using a rotary evaporator, and 72g (0.134mol) of the target product was recovered. [ka] 2. Acrylic esterification of the amide compound of CAE-600 and MEA (fluoromonomer A) The amide compound of CAE-600 and MEA (31.7 g, 0.0589 mol), ethyl acetate (31.7 g), and triethylamine (7.13 g, 0.0706 mol) were placed in a 100 mL eggplant flask equipped with a stirrer. Acrylic acid chloride (5.86 g, 0.0648 mol) was added dropwise in a water bath and stirred at room temperature for 4 hours. Water was added to the reaction liquid, which was then stirred and separated. The organic layer was concentrated using a rotary evaporator, and 29.2 g (0.0492 mol) of fluoromonomer A was recovered. [ka] The 1H NMR of the obtained fluoromonomer A is shown below: 1 H-NMR(CDCl3)δ(ppm): 3.7ppm(2H, m), 4.3ppm(2H,t), 5.9ppm(1H, dd), 6.1ppm(1H, dd), 6.5ppm(1H, dd), 6.9ppm(1H, br)

[0057] Synthesis Example 2: Synthesis of fluoromonomer B Fluorine monomer B was obtained in the same manner as in Synthesis Example 1, except that methacrylic acid chloride was used instead of acrylic acid chloride. [ka] The 1H NMR of the obtained fluoromonomer B is shown below: 1 H-NMR(CDCl3)δ(ppm): 1.9ppm(3H, s), 3.7ppm(2H, m), 4.3ppm(2H,m), 5.6ppm(1H, dd), 6.1ppm(1H, s), 6.9ppm(1H, br)

[0058] Production Example 1: Synthesis of copolymer Fluorine monomer A (3.73g, 0.00629mol), Cyclomer M100 (1.82g, 0.00928mol), AE-400 (4.84g, 0.00945mol), ethyl acetate (15g), dodecanethiol (0.61g, 0.00302mol), and V-601 (0.17g, 0.000739mol) were added to a 50mL three-neck flask equipped with a stirrer, and the reaction solution was stirred for 30 minutes while bubbling with nitrogen. The reaction solution was heated to 70°C and stirred for 5 hours.

[0059] Manufacturing Examples 2-4 Copolymers of Production Examples 2 to 4 were synthesized in the same manner as in Production Example 1, except that the types and amounts of monomers shown in the following Table 1 were used. The numbers in parentheses indicate % by weight. [Table 1]

[0060] Examples 1 to 3, Comparative Example 1 The synthesized copolymer was added to U-Varnish A (polyimide resin, UBE Corporation, solid content 20 wt%) diluted with DMF to a solid content concentration of 5%, at 1% solid content (0.05% in the coating liquid). It was applied to a 10 cm square glass plate using a spin coater (500 rpm, 10 seconds), heated at 110°C for 3 minutes, and the coating was dried. It was then heated at 250°C for 60 minutes to harden the coating. The resulting coating film was evaluated by the following methods.

[0061] Evaluation method ·Contact angle The contact angles of anisole dropped onto the coating film after drying after heating at 110°C for 3 minutes and the coating film after curing after heating at 250°C for 60 minutes were measured using a DMo-702 (manufactured by Kyowa Interface Science Co., Ltd.) If the difference was less than 5°, it was rated as A, if it was less than 10°, it was rated as B, and if it was 10° or more, it was rated as C. ·Heat resistance The thermal weight loss of the synthesized polymer after heating at 250°C for 60 minutes was measured using a NEXTA STA200RV (Hitachi High-Tech Science Corporation). Weight loss of 20 wt% or less was rated A, weight loss of less than 30 wt% was rated B, and weight loss of 30 wt% or more was rated C. The evaluation results are shown in Table 1 above.

[0062] As shown in Table 1, when the liquid-repellent compositions containing the copolymers of Production Examples 1 to 3 were used, the change in contact angle of the coating film was small and the heat resistance was high even when the coating was cured in a high-temperature process (200 to 280°C). Therefore, it was revealed that the liquid-repellent agent of the present invention is preferable as a liquid-repellent agent that imparts liquid repellency to a thermosetting resin composition.

Claims

1. The following (A) to (C) (A) (Meth)acrylate Monomer Containing a Perfluoroether Moiety and an Amide Bond (B) Epoxy group-containing (meth)acrylate monomer (C) Hydroxyl group-containing (meth)acrylate monomer A copolymer of monomers comprising:

2. The copolymer according to claim 1, wherein the (meth)acrylate monomer containing a perfluoroether moiety and an amide bond is represented by the following formula (A1): 【Chemistry 1】 [In the formula, R １ represents a hydrogen or a methyl group. R ２ represents a divalent saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms (the saturated aliphatic hydrocarbon group may be linear or branched, and may have an ether bond (-O-) or an ester bond (-CO-O- or -O-CO-)). n represents an integer of 0 to 10.

3. 2. The copolymer according to claim 1, wherein the (meth)acrylate monomer containing a perfluoroether moiety and an amide bond has a molecular weight of 400 to 2,200.

4. The copolymer according to claim 1, having a fluorine content of 5 to 40% by mass.

5. A liquid repellent comprising the copolymer according to any one of claims 1 to 4.

6. The liquid repellent according to claim 5 , which is dissolved in a solvent.

7. The liquid repellent according to claim 5, which is added to a thermosetting resin.

8. A liquid repellent composition comprising a thermosetting resin and the liquid repellent agent according to claim 5.

9. A liquid-repellent cured resin which is a cured product of the liquid-repellent composition according to claim 8.

10. An article comprising the liquid repellent cured resin according to claim 9.

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