Fluorine-containing copolymers, surface modifiers, leveling agents, coating agents, and articles

Abstract

To provide a material that is excellent in terms of recoating (lamination) and leveling.SOLUTION: A fluorinated copolymer contains (i) a repeat unit derived from a fluorinated methacrylate monomer (A) represented by the formula (I) and (ii) a repeat unit derived from a specific methacrylamide monomer (B) and / or a specific methacrylate hydrophobic monomer (C) (where R1 is a hydrogen atom or a methyl group. Y1 is a divalent linking group. Rf is a specific perfluoroalkyl group).SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to fluorine-containing copolymers, surface modifiers, leveling agents, coating agents, and articles. [Background technology]

[0002] In image display devices such as plasma displays (PDPs), electroluminescent displays (ELDs), fluorescent displays (VFDs), field emission displays (FEDs), and liquid crystal displays (LCDs), it is preferable to provide a hard coat layer on the surface to prevent scratches on the display surface.

[0003] With the diversification of image display devices, such as touch panels, there is a growing demand for laminating (recoating) other functional layers onto the hard coat layer. This necessitates a hard coat layer that is easy to laminate with other layers, i.e., has excellent lamination (recoating) properties. When recoating onto a hard coat layer, if the wettability of the hard coat layer surface is not high, uneven coating due to repelling or uneven coating thickness can occur, impairing the smoothness of the surface.

[0004] However, on the other hand, hard coat layers typically contain leveling agents such as fluorine-containing polymers to improve the homogeneity of the coating film itself. The hydrophobicity of these leveling agents causes the surface of the hard coat layer to become hydrophobic. Thus, a trade-off between the homogeneity of the hard coat layer and its recoatability becomes a problem.

[0005] Patent Document 1 discloses a fluorine-containing pyrolytic surfactant as a leveling agent that combines recoating properties and homogeneity. However, when this surfactant is used, a pyrolysis step of the leveling agent is required to achieve recoating properties, and there is a drawback that the use of the leveling agent is limited by the heat resistance of the substrate.

[0006] Patent Document 2 discloses the use of a fluorine-containing polymer obtained by polymerizing a fluorine-containing monomer and an acrylamide compound for water-repellent and oil-repellent applications.

Prior Art Documents

Patent Documents

[0007]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0008] The main object of the present invention is to provide a material excellent in recoatability (laminability) and leveling property.

Means for Solving the Problems

[0009] The present invention provides the following fluorine-containing copolymer, surface conditioner, leveling agent, coating agent, and article. Item 1. (i) A repeating unit derived from the following monomer (A) and (ii) a fluorine-containing copolymer containing a repeating unit derived from monomer (B) and / or monomer (C): (A) A fluorine-containing (meth)acrylate monomer represented by the following formula (I)

[0010]

Chemical Formula

[0011] (In the formula, R

[0013] , represents a hydrogen atom or a methyl group. Y 1 represents a divalent linking group. Rf is a perfluoroalkyl group represented by the following formula (1) or the following formula (2) ​​​​​​​​​​​​(B) A (meth)acrylamide-based monomer represented by the following formula (II):

[0014] [Chemical formula]

[0015] (In the formula, R 2 represents a hydrogen atom or a methyl group. R 3 , R 4 are the same or different and each represents an alkyl group having 1 to 6 carbon atoms.) (C) A hydrophobic monomer represented by the following formula (III). <00001却表示出了一种完全不同的情况。

[0016] [Chemical formula]

[0017] (In the formula, R 5 represents a hydrogen atom or a methyl group. R 6 represents an optionally substituted alkyl group having 1 to 30 carbon atoms, an optionally substituted cycloalkyl group having 3 to 30 carbon atoms, an optionally substituted aryl group having 6 to 30 carbon atoms, or an optionally substituted aralkyl group having 7 to 30 carbon atoms.) Item 2. The fluorine-containing copolymer according to Item 1, comprising a repeating unit derived from monomer (A), a repeating unit derived from monomer (B), and a repeating unit derived from monomer (C). Item 3. The fluorine-containing copolymer according to Item 1 or 2, wherein the mass ratio of monomer (B) to monomer (A) {mass of monomer (B) / mass of monomer (A)} is 1 to 20. Item 4. The fluorine-containing copolymer according to Item 1 or 2, wherein the mass ratio of monomer (C) to monomer (A) {mass of monomer (C) / mass of monomer (A)} is 1 to 20. Item 5. A surface conditioner composed of the fluorine-containing copolymer according to any one of Items 1 to 4. Item 6. A leveling agent composed of the fluorine-containing copolymer according to any one of Items 1 to 4. Item 7. A coating agent comprising a UV-curing resin, a coating polymer, or a thermosetting resin and a fluorine-containing copolymer as described in any of Items 1 to 4. Article 8. An article comprising a layer formed using the coating agent described in Article 7. [Effects of the Invention]

[0018] The fluorine-containing compound of the present invention, when incorporated into a coating agent for forming an intermediate layer such as an interlayer film or primer layer on which a functional layer is laminated, can achieve a high level of both leveling properties of the coating agent and recoatability (lamination properties) of the coating layer.

[0019] The fluorine-containing copolymer, surface modifier, and leveling agent of the present invention can be suitably used as additives to film coating liquids, paints, liquid crystals, etc., and the coating agent of the present invention can provide a surface state that allows another layer to be coated on top of the coating while maintaining the leveling properties of the coating. [Modes for carrying out the invention]

[0020] The fluorine-containing copolymer of the present invention comprises the following three fluorine-containing copolymers (x) to (z): (x) A fluorine-containing copolymer containing repeating units derived from monomer (A) and repeating units derived from monomer (B), (y) A fluorine-containing copolymer containing repeating units derived from monomer (A) and repeating units derived from monomer (C), (z) A fluorine-containing copolymer containing repeating units derived from monomer (A), repeating units derived from monomer (B), and repeating units derived from monomer (C).

[0021] Monomer (A) is a fluorine-containing (meth)acrylate monomer represented by the following formula (I). Monomer (A) may be used alone or in combination of two or more types.

[0022] [ka]

[0023] (In the formula, R 1 represents a hydrogen atom or a methyl group. Y 1 represents a divalent linking group. Rf is represented by the following formula (1) or the following formula (2)

[0024] [Chemical formula]

[0025] and represents a perfluoroalkyl group.)

[0026] R 1 is a hydrogen atom or a methyl group, preferably a hydrogen atom.

[0027] Y 1 Examples of the divalent linking group represented by include a linear, branched or cyclic alkylene group having 1 to 20 carbon atoms, an optionally substituted arylene group, and an optionally substituted aralkylene group. Between two adjacent carbon atoms of the divalent linking group, an ether bond (-O-), an ester bond (-COO- or -O-CO-), or an amide bond (-NHCO- or -CONH-) may be interposed. For example, those in which the above bonds are interposed in a butylene group include -CH2CH2-O-CH2CH2-, -CH2CH2-O-CO-CH2CH2-, -CH2CH2-CO-O-CH2CH2-, -CH2CH2-CONH-CH2CH2-, -CH2CH2-NHCO-CH2CH2-.

[0028] Examples of the alkylene group having 1 to 20 carbon atoms and being linear or branched include -(CH2) m - (m is an integer from 1 to 20), -CH(CH3)CH2-, -CH2CH(CH3)-, -CH(CH2CH3)CH2-, -CH2CH(CH2CH3)-, and the like.

[0029] Examples of cyclic alkylene groups having 1 to 20 carbon atoms include cyclopropylene, 1,3-cyclopentylene, 1,2-cyclohexylene, 1,3-cyclohexylene, and 1,4-cyclohexylene.

[0030] Examples of arylene groups include phenylene groups, biphenylene groups, phenoxyphenylene groups, naphthylene groups, anthracenylene groups, phenantrenylene groups, and fluorenylene groups.

[0031] Examples of aralkylene groups include the benzylene group and the phenethylene group.

[0032] The number of substituents on the arylene group and aralkylene group is preferably 1 to 3, more preferably 1 to 2. Examples of substituents include methoxy group, ethoxy group, methyl group, ethyl group, chlorine atom, -CN, -NO2, OH, acetyl group, acetylamino group, and carbamoyl group.

[0033] Y 1 Preferred divalent linking groups represented by the following include: -(CH2) n1 -, (n1=2~10), -CH(CH3)CH2-, -CH2CH(CH3)-, -CH(CH2CH3)CH2-, -CH2CH(CH2CH3)-, -(CH2CH2O) n2 -CH2CH2-, (n2=1~9) -CH2CH2O-CO-(C6H4)-, -CH2CH2-CO-O-(C6H4)-, -CH2CH2O-CO-(CH2CH2)-, -CH2CH2-CO-O-(CH2CH2)-, -CH2CH2O-CO-(cyclohexylene group)-, -CH2CH2-CO-O-(cyclohexylene group)-.

[0034] The above acrylamide monomer (B) is preferably represented by the following formula (II):

[0035] [ka]

[0036] (In the formula, R 2 R represents a hydrogen atom or a methyl group. 3 , R 4 (This represents an alkyl group having 1 to 6 carbon atoms, which may be the same or different.)

[0037] R 2 This is a hydrogen atom or a methyl group, preferably a hydrogen atom.

[0038] In acrylamide monomer (B), R 3 , R 4 Examples of alkyl groups having 1 to 6 carbon atoms, represented by , include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, and hexyl group.

[0039] The acrylamide monomer (B) may be used alone or in combination of two or more types.

[0040] The hydrophobic monomer (C) is preferably represented by the following formula (III):

[0041] [ka]

[0042] (In the formula, R 5 R represents a hydrogen atom or a methyl group. 6 This represents an optionally substituted alkyl group having 1 to 30 carbon atoms, an optionally substituted cycloalkyl group having 3 to 30 carbon atoms, an optionally substituted aryl group having 6 to 30 carbon atoms, or an optionally substituted aralkyl group having 7 to 30 carbon atoms.

[0043] R 5 This is a hydrogen atom or a methyl group, preferably a methyl group.

[0044] R 6 Examples of alkyl groups having 1 to 30 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group, icosyl group, henaicosyl group, docosyl group, and triacontyl group.

[0045] The number of substituents on a C1-C30 substituted alkyl group is preferably 1-3, more preferably 1-2. Examples of substituents on a C1-C30 substituted alkyl group include halogen atoms, -CN, -NO2, -OH, acetyl groups, acetylamino groups, and carbamoyl groups.

[0046] Examples of cycloalkyl groups having 3 to 30 carbon atoms include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl groups.

[0047] The number of substituents on a substituted cycloalkyl group having 3 to 30 carbon atoms is preferably 1 to 3, more preferably 1 to 2. Examples of substituents include alkyl groups having 1 to 10 carbon atoms, halogen atoms, -CN, -NO2, -OH, acetyl groups, acetylamino groups, and carbamoyl groups. Examples of alkyl groups having 1 to 10 carbon atoms include methyl groups, ethyl groups, n-propyl groups, isopropyl groups, n-butyl groups, isobutyl groups, sec-butyl groups, t-butyl groups, pentyl groups, hexyl groups, heptyl groups, octyl groups, nonyl groups, and decyl groups.

[0048] Examples of aryl groups having 6 to 30 carbon atoms include phenyl, biphenyl, phenoxyphenyl, naphthyl, anthracenyl, phenantrenyl, and fluorenyl groups.

[0049] Examples of aralkyl groups with 7 to 30 carbon atoms include the benzyl group and the phenethyl group.

[0050] The number of substituents on the substituted aryl group having 6 to 30 carbon atoms and the substituted aralkyl group having 7 to 30 carbon atoms is preferably 1 to 3, more preferably 1 to 2. Examples of substituents include methoxy, ethoxy, methyl, ethyl, chlorine, -CN, -NO2, -OH, acetyl, acetylamino, and carbamoyl groups.

[0051] The hydrophobic monomer (C) may be used alone or in combination of two or more types.

[0052] The fluorine-containing copolymer of the present invention may be prepared by copolymerizing (i) monomer (A), (ii) monomer (B) and / or monomer (C) with (iii) an optional monomer (D). Examples of monomer (D) include ethylene, propylene, acrylonitrile, methacrylonitrile, vinyl acetate, (meth)acrylic acid ester, acrylamide, and methacrylamide. Examples of (meth)acrylic acid esters 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.

[0053] Monomer (D) may be used alone or in combination of two or more types.

[0054] The weight-average molecular weight of the fluorine-containing copolymer of the present invention is preferably 3,000 to 50,000, more preferably 10,000 to 20,000. The weight-average molecular weight can be calculated by converting it to the molecular weight of standard polystyrene using gel permeation chromatography (GPC).

[0055] The proportions of repeating units derived from monomer (A), monomer (B), monomer (C), and monomer (D) used to obtain the fluorine-containing copolymer of the present invention are as follows, with the total amount of solids contained in the blended composition being 100% by mass. Repeating units derived from monomer (A): Preferably 3 to 60% by mass, more preferably 4 to 50% by mass, even more preferably 6 to 40% by mass, and most preferably 8 to 30% by mass. Repeating units derived from monomer (B): Preferably 0-95% by mass, more preferably 5-85% by mass, even more preferably 15-70% by mass, and most preferably 25-60% by mass. Repeating units derived from monomer (C): Preferably 0-95% by mass, more preferably 5-85% by mass, even more preferably 15-70% by mass, and most preferably 25-60% by mass. Repeating units derived from monomer (D): Preferably 0 to 30% by mass, more preferably 0 to 20% by mass, even more preferably 0 to 10% by mass, and most preferably 0 to 5% by mass.

[0056] In the fluorine-containing copolymer of the present invention, which includes repeating units derived from monomer (A) and monomer (B), such as monomer (A) + monomer (B), or monomer (A) + monomer (B) + monomer (C), the mass ratio of monomer (A) to monomer (B) {mass of monomer (B) / mass of monomer (A)} is preferably 1 to 20, more preferably 1.5 to 15, even more preferably 2 to 10, and most preferably 3 to 8.

[0057] In the fluorine-containing copolymer of the present invention, which includes repeating units derived from monomer (C) and monomer (A), such as monomer (C) + monomer (A), or monomer (C) + monomer (A) + monomer (B), the mass ratio of monomer (C) to monomer (A) {mass of monomer (C) / mass of monomer (A)} is preferably 1 to 20, more preferably 1.5 to 15, even more preferably 2 to 10, and most preferably 3 to 8.

[0058] The surface modifier and leveling agent of the present invention, when added to a coating agent for forming an interlayer or intermediate layer containing a UV-curing resin or coating polymer, allows the coating agent to spread evenly without repelling when applied to a substrate, enabling application to the substrate (base material). When cured to form a film, it exhibits good surface smoothness (leveling properties). As a result, the upper layer of the overcoat or topcoat layer formed on the interlayer or intermediate layer achieves a certain degree of smoothness.

[0059] The amount of the surface modifier or leveling agent of the present invention added to the coating agent is preferably 10 to 5000 ppm, more preferably 30 to 3000 ppm, even more preferably 50 to 2000 ppm, and particularly preferably 70 to 1000 ppm. When the coating agent contains a UV-curing resin or a coating polymer, the fluorine-containing copolymer is blended to the above specified concentration relative to the weight of solids excluding the initiator. When the coating agent contains a thermoplastic resin, the fluorine-containing copolymer is blended to the above specified concentration relative to the total weight of solids. When the amount of surface modifier or leveling agent added is 5000 ppm or less, the coating properties are good, and when the amount added is 10 ppm or more, the leveling properties are good.

[0060] Fluorine-containing copolymers can be obtained by copolymerizing (i) monomer (A), (ii) monomer (B) and / or monomer (C), and (iii) an optional monomer (D). The copolymerization reaction proceeds favorably by reacting at 40-90°C for 4-12 hours in the presence of a radical initiator. Examples of radical initiators 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, and 2,5-dimethyl-2,5-di(t -Butylperoxy)-hexine-3-acetyl peroxide, succinate peroxide, diisobutyryl peroxide, lauroyl peroxide, benzoyl peroxide, t-butyl peroxyacetate, t-butyl peroxyisobutyrate, di-isobutyl peroxydicarbonate, t-butyl peroxyisopropyl carbonate, methyl ethyl ketone peroxide, cyclohexanone peroxide, 2,2'-azobisisobutyronitrile, dimethyl=2,2'-azobisisobutyrate, Examples of azo compounds include 2,2'-azobis(2-methylpropionic acid)dimethyl (V-601), 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(isobutylamidine) dihydrochloride, 2,2'-azobis[2-(2-imidazolin-2-yl)propane] and its disulfate, and 2,2'-azobis(2-methylamidooxime) dihydrochloride; potassium persulfate, sodium persulfate, ammonium persulfate, potassium persulfate, t-butyl hydroperoxide, benzoyl peroxide, and cumene hydroperoxide. These radical polymerization initiators may be used individually or in combination of two or more.The copolymerization reaction may also involve adjusting the molecular weight using chain transfer agents such as dodecanethiol, octyl mercaptan, dodecyl mercaptan, 2-mercaptoethanol, octyl thioglycolate, 3-mercaptopropionic acid, and thioglycerin.

[0061] The fluorine content of the fluorine-containing copolymer is preferably 2 to 40% by mass, more preferably 3 to 35% by mass, even more preferably 4 to 25% by mass, and most preferably 5 to 15%, based on the total amount of solids in the blended composition as 100% by mass. When the fluorine content is 40% by mass or less, the coating properties are good, and when the fluorine content is 2% by mass or more, the leveling properties are good.

[0062] The coating agent to which the surface modifier or leveling agent of the present invention is added usually contains a solvent. Examples of 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 (PG). Examples include MEA, 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, 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, and 1,4-dioxane.

[0063] Examples of UV-curing resins include acrylic resins, epoxy resins, and melamine resins. One preferred embodiment of the UV-curing resin is used in the manufacture of color filters, color resists, and the like. The color resist includes resists for the manufacture of black matrices (black resists). The UV-curing resin may be a bifunctional or more curing resin to satisfy physical properties such as heat resistance, hot water resistance, and chemical resistance. UV-curing resins that exhibit low molecular weight and amorphous properties are preferred when obtaining low viscosity, liquid coating agents.

[0064] Examples of coating polymers include poly(meth)acrylate-based, polyoxyalkylene-based, polyurethane-based, poly(meth)acrylamide-based, polyester-based, polyamide-based, polyamine-based, and polyvinyl-based polymers, which can be included individually or in combination of two or more.

[0065] Examples of thermosetting resins that can be used include epoxy resins, urea resins, melamine resins, phenolic resins, unsaturated polyester resins, alkyd resins, and urethane resins.

[0066] A cured resin layer can be obtained by applying the coating liquid of the present invention to a substrate and curing it by UV (ultraviolet) irradiation or heat treatment as needed. Curing can be carried out under curing conditions for UV-curable resins or thermosetting resins. In one preferred embodiment, an article having an interlayer film can be obtained by applying the liquid coating agent of the present invention to a substrate and curing it with UV or heat as needed. Examples of substrates include silicon wafers, synthetic resins, glass, metals, and ceramics. The synthetic resin may be either a thermoplastic resin or a thermosetting resin. Examples of glass include silicate glass, alkali silicate glass, soda-lime glass, potassium-lime glass, lead glass, barium glass, and borosilicate glass. Examples of metals 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), and carbides (e.g., silicon carbide).

[0067] For applying the coating agent to the substrate, various methods can be employed, such as roll coating, gravure coating, microgravure coating, flow coating, bar coating, spray coating, die coating, spin coating, and dip coating. The method can be selected considering the type and shape of the substrate, productivity, and controllability of the film thickness.

[0068] The layer (cured resin layer) formed using the coating agent of the present invention exhibits excellent lamination properties (recoatability). Generally, if the surface free energy of the coating liquid and the surface free energy of the object to be coated are approximately the same, the coating liquid will spread easily on the surface of the object to be coated, and uneven coating will not occur. The surface free energy of the layer (cured resin layer) formed using the coating agent of the present invention is 30-50 mJ / m 2This can be controlled. Many common solvents, such as alcohols and ketones, have a surface free energy similar to that of the cured resin layer. Therefore, even with a coating liquid using a common solvent, it is possible to wet and spread the coating film on the surface of the cured resin layer and laminate (recoat) it, without using special solvents with low surface free energy, such as fluorine-based solvents. [Examples]

[0069] The present invention will be described in detail below with reference to examples.

[0070] The following monomers were used in the examples and comparative examples.

[0071] [ka]

[0072] (However, Rf is given by either formula (1) or formula (2) below)

[0073] [ka]

[0074] (This represents a perfluoroalkyl group represented by [the symbol].)

[0075] [Preparation of coating solution] Coating liquid A: UV-curing resin (polyfunctional acrylate, urethane acrylate) Coating liquid B: Thermosetting resin (epoxy resin, epoxy acrylate) A specified amount of additive (1000 ppm of active ingredient relative to the resin) was added to obtain coating solution A or coating solution B.

[0076] [Preparation of the hardened film] Spin coating method: A film was formed on a glass plate by spin coating (rotation speed 1000 rpm, 10 sec), and cured with UV light or heat to obtain a cured film.

[0077] [Evaluation of the hardened film] ◆Recoatability The contact angles of the cured film with water and diiodomethane were measured, and the surface free energy was calculated. The surface free energy was calculated by applying the results of the ion-exchanged water contact angle and diiodomethane contact angle to the Kaelble-Uy method. ○: Surface free energy value is 30-50 mJ / m 2 Within the range ×: Surface free energy outside the above range ◆ Coatability (leveling properties) The appearance of the hardened coating was visually inspected. ○: Good appearance ×: Cosmetic defects (uneven coating, paint defects, blemishes, etc.)

[0078] Example 1 (1) Synthesis of fluorine-containing copolymers In a two-necked round-bottom flask, 0.55 g of fluorine monomer A1 (manufactured by Neos Co., Ltd.), 10.40 g of diethylacrylamide (DEAA), 0.67 g of 2,2'-azobis(2-methylpropionic acid)dimethyl (V-601) as a polymerization initiator, 0.38 g of dodecanethiol as a polymerization regulator, and 28.00 g of propylene glycol monomethyl ether acetate (PGMEA) as a solvent were added. The reaction mixture was stirred for 30 minutes while bubbling with nitrogen. The reaction mixture was heated to 80°C and stirred at 80°C for 5 hours.

[0079] After the reaction was complete, 4.00 g of propylene glycol monomethyl ether acetate was added to the reaction mixture so that the solid content concentration was 30%, and a fluorine-containing copolymer was obtained.

[0080] (2) Preparation of coating solution Coating liquid A: 25.0 g of urethane acrylate (UA-510H), 10.0 g of polyfunctional acrylate (NK ester A-9550W), 0.88 g of photocuring initiator (Irgacure 369), and 64.12 g of propylene glycol monomethyl ether acetate were stirred. The fluorine-containing copolymer was added to the resin to a concentration of 1000 ppm of active ingredients to prepare a photocurable coating solution. Coating liquid B: 7.5 g of epoxy resin (Epicote 828), 7.5 g of carboxylic acid anhydride (Kayahard MCD), 5.0 g of epoxy acrylate (epoxy ester 3000A), and 80.00 g of propylene glycol monomethyl ether acetate were stirred. A fluorine-containing copolymer was added to the resin to a concentration of 1000 ppm of active ingredients to prepare a thermosetting coating solution.

[0081] (3) Coating conditions Spin court: The coating solution was spun-coated onto a 4cm square glass plate at a rotation speed of 1000 rpm for 10 seconds.

[0082] (4) Curing conditions UV light: High-pressure mercury lamp: 500 mJ / cm² 2 A cured film was obtained by exposure under the following conditions. heat: The film was dried at 90°C for 100 seconds to remove the solvent, and then heated at 200°C for 30 minutes to obtain a cured film.

[0083] (Examples 2-50, Comparative Examples 1-12) A cured film was manufactured in the same manner as in Example 1, except that the composition of the compositional mixture was as shown in Table 1.

[0084] Examples 1-50, Comparative Examples 1-12 Examples 1-50 exhibit good leveling and recoatability. Comparative Examples 1-4 and 7-10, with low fluorine content, show insufficient leveling. Comparative Examples 5, 6, 11, and 12, with excessively high fluorine monomer content, do not dissolve in the coating solution and remain on the coating film as foreign matter, reducing both leveling and recoatability.

[0085] [Table 1]

[0086] [Table 2]

[0087] Table 3

Claims

1. (i) Repeating units derived from the monomer (A) below (ii) A fluorine-containing copolymer containing repeating units derived from monomer (B), wherein the mass ratio of monomer (A) to monomer (B) {mass of monomer (B) / mass of monomer (A)} is 1 to 20: (A) Fluorine-containing (meth)acrylate monomers represented by the following formula (I) 【Chemistry 1】 (In the formula, R １ Y represents a hydrogen atom or a methyl group. １ represents a divalent linking group. Rf is represented by the following formula (1) or formula (2). 【Chemistry 2】 (This represents a perfluoroalkyl group represented by [the symbol].) (B) (meth)acrylamide monomer represented by the following formula (II), 【Transformation 3】 (In the formula, R ２ R represents a hydrogen atom or a methyl group. ３ , R ４ (These represent alkyl groups having 1 to 6 carbon atoms, which are the same or different.)

2. (i) Repeating units derived from the monomer (A) below (ii) Repeating units derived from monomer (B) (iii) Fluorine-containing copolymers containing repeating units derived from monomer (C): (A) Fluorine-containing (meth)acrylate monomers represented by the following formula (I) 【Chemistry 1】 (In the formula, R1 represents a hydrogen atom or a methyl group. Y1 represents a divalent linking group. Rf is the following formula (1) or formula (2)) 【Chemistry 2】 (This represents a perfluoroalkyl group represented by [the symbol].) (B) (meth)acrylamide monomer represented by the following formula (II), 【Transformation 3】 (In the formula, R2 represents a hydrogen atom or a methyl group. R3 and R4 are the same or different alkyl groups having 1 to 6 carbon atoms.) (C) A hydrophobic monomer represented by the following formula (III). 【Chemistry 4】 (In the formula, R 5 represents a hydrogen atom or a methyl group. R 6 represents an optionally substituted alkyl group having 1 to 30 carbon atoms, an optionally substituted cycloalkyl group having 3 to 30 carbon atoms, an optionally substituted aryl group having 6 to 30 carbon atoms, or an optionally substituted aralkyl group having 7 to 30 carbon atoms.)

3. The fluorine-containing copolymer according to claim 2, wherein the mass ratio of monomer (A) to monomer (B) {mass of monomer (B) / mass of monomer (A)} is 1 to 20.

4. The fluorine-containing copolymer according to claim 2, wherein the mass ratio of monomer (C) to monomer (A) {mass of monomer (C) / mass of monomer (A)} is 1 to 20.

5. A surface modifier comprising a fluorine-containing copolymer according to claim 1 or 2.

6. A leveling agent comprising a fluorine-containing copolymer according to claim 1 or 2.

7. A coating agent comprising a UV-curing resin, a coating polymer, or a thermosetting resin and the fluorine-containing copolymer described in claim 1 or 2.

8. An article comprising a layer formed using the coating agent described in claim 7.

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