JP7854866B2 - Fluorine-containing copolymers, surface modifiers, leveling agents, coating agents, and articles - Google Patents

Description

This invention relates to fluorine-containing copolymers, surface modifiers, leveling agents, coating agents, and articles.

In image display devices such as plasma displays (PDPs), electroluminescent displays (ELDs), fluorescent display 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.

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. Therefore, there is a need for 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 surface smoothness.

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 hard coat surface to become hydrophobic. Thus, a trade-off between the homogeneity of the hard coat layer and its recoatability becomes a problem.

Patent Document 1 discloses a fluorine-containing pyrolytic surfactant as a leveling agent that combines recoating properties and homogeneity. However, when using this surfactant, a pyrolysis step of the leveling agent is required to achieve recoating properties, which has the drawback of limiting the use of the leveling agent depending on the heat resistance of the substrate.

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.

Patent No. 6025008 WO2009/123006

The main objective of this invention is to provide a material with excellent recoatability (lamination properties) and leveling properties.

The present invention provides the following fluorine-containing copolymers, surface modifiers, leveling agents, coating agents, and articles.
Item 1. (i) Repeating units derived from monomer (A) and (ii) Repeating units derived from monomer (B) and/or monomer (C) below, comprising a fluorine-containing copolymer:
(A) Fluorine-containing (meth)acrylate monomers represented by the following formula (I)

(In the formula, ^R1 represents a hydrogen atom or a methyl group. ^Y1 represents a divalent linking group. Rf is either formula (1) or formula (2) below.)

(This represents a perfluoroalkyl group represented by [the symbol].)
(B) (meth)acrylamide monomer represented by the following formula (II),

(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).

(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 repeating units derived from monomer (A), repeating units derived from monomer (B), and repeating units derived from monomer (C).
Item 3. The fluorine-containing copolymer according to item 1 or 2, wherein the mass ratio of monomer (A) to monomer (B) {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 modifier comprising a fluorine-containing copolymer as described in any one of items 1 to 4.
Item 6. A leveling agent comprising a fluorine-containing copolymer as described in 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.
Item 8. An article comprising a layer formed using the coating agent described in Item 7.

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.

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. The coating agent of the present invention can provide a surface state that allows for the coating of another layer while maintaining the leveling properties of the coating.

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 comprising repeating units derived from monomer (A), repeating units derived from monomer (B), and repeating units derived from monomer (C).

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.

(In the formula, R ¹ represents a hydrogen atom or a methyl group. ^{Y 1} represents a divalent linking group. Rf is either formula (1) or formula (2) below.)

(This represents a perfluoroalkyl group.)

^R1 is a hydrogen atom or a methyl group, preferably a hydrogen atom.

Examples of divalent linking groups represented by ^Y1 include linear, branched, or cyclic alkylene groups having 1 to 20 carbon atoms, optionally substituted arylene groups, and optionally substituted aralkylene groups. The two adjacent carbon atoms of the divalent linking group may be interposed by an ether bond (-O-), an ester bond (-COO- or -O-CO-), or an amide bond (-NHCO- or -CONH-). For example, those in which the above bonds are interposed on a butylene group include _{-CH2CH2 - O-CH2CH2-, -CH2CH2 - O - CO} - _{CH2CH2- , -CH2CH2 -} CO-O _{- CH2CH2-} , _-CH2CH2 - _CONH -CH2CH2- _{, and -CH2CH2} - _NHCO - _CH2CH2- .

Examples of linear or branched alkylene groups having 1 to 20 carbon atoms include -( _CH2 ) _m- (where m is an integer from 1 to 20), -CH( _CH3 ) _CH2- , _{-CH2CH ( CH3} )-, -CH( _CH2CH3 ) _CH2- , and _-CH2CH ( _CH2CH3 ) _- .

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.

Examples of allerene groups include phenylene, biphenylene, phenoxyphenylene, naphthylene, anthracenylene, phenantrenylene, and fluorenylene.

Examples of aralkylene groups include the bendiylene group and the phenethylene group.

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.

Preferred divalent linking groups represented by ^Y1 include the following:
-(CH ₂ ) _n1 -, (n1=2 to 10),
-CH( _CH3 ) _CH2- , _-CH2CH ( _CH3 )-,
-CH(CH ₂ CH ₃ )CH ₂ -, -CH ₂ CH(CH ₂ CH ₃ )-,
-(CH ₂ CH ₂ O) _n2 -CH ₂ CH ₂ -, (n2=1 to 9),
-CH ₂ CH ₂ O-CO-(C ₆ H ₄ )-,
-CH ₂ CH ₂ -CO-O-(C ₆ H ₄ )-,
-CH ₂ CH ₂ O-CO-(CH ₂ CH ₂ )-,
-CH ₂ CH ₂ -CO-O-(CH ₂ CH ₂ )-,
_-CH₂CH₂O -CO-( _{cyclohexylene} group)-
_{-CH₂CH₂ -} CO-O-(cyclohexylene group)-.

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

(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.)

^R2 is a hydrogen atom or a methyl group, preferably a hydrogen atom.

In the acrylamide monomer (B), examples of alkyl groups having 1 to 6 carbon atoms represented by ^R3 and ^R4 include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, and hexyl groups.

Acrylamide monomer (B) may be used alone or in combination of two or more types.

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

(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.)

^R5 is a hydrogen atom or a methyl group, preferably a methyl group.

Examples of alkyl groups with 1 to 30 carbon atoms in R ⁶ 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.

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.

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

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.

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

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

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.

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

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.

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

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).

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 to 95% by mass, more preferably 5 to 85% by mass, even more preferably 15 to 70% by mass, and most preferably 25 to 60% by mass.
Repeating units derived from monomer (C): Preferably 0 to 95% by mass, more preferably 5 to 85% by mass, even more preferably 15 to 70% by mass, and most preferably 25 to 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.

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.

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.

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. When cured, it forms a film with 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.

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 specified concentration relative to the weight of the solids excluding the initiator. When the coating agent contains a thermoplastic resin, the fluorine-containing copolymer is blended to the specified concentration relative to the total weight of the solids. A surface modifier or leveling agent addition of 5000 ppm or less results in good coating properties, while an addition of 10 ppm or more results in good leveling properties.

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 to 90°C for 4 to 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)-hexyne-3-acetyl peroxide, succinate peroxide, diisobutyryl peroxide, lauroyl peroxide, benzoyl peroxide, t-butyl peroxyacetate, t-butyl peroxyisobutyrate, diisobutyl 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.

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. A fluorine content of 40% by mass or less results in good coating properties, while a fluorine content of 2% by mass or more results in good leveling properties.

The coating agent to which the surface modifier or leveling agent of the present invention is added usually contains a solvent. The 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.

As the UV-curing resin, acrylic resins, epoxy resins, melamine resins, etc., can be used. One preferred embodiment of the UV-curing resin is used in the manufacture of color filters, color resists, etc. The color resist includes resists for black matrix production (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. For obtaining a low-viscosity, liquid coating agent, it is preferable to use a UV-curing resin that exhibits low molecular weight and amorphous properties.

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

Suitable thermosetting resins include epoxy resins, urea resins, melamine resins, phenolic resins, unsaturated polyester resins, alkyd resins, and urethane resins.

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 the 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 by UV or heat curing as needed. Examples of substrates include silicon wafers, synthetic resins, glass, metals, and ceramics. Synthetic resins may be either thermoplastic resins or thermosetting resins. 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).

The coating agent can be applied to the substrate using various methods, 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 factors such as the type and shape of the substrate, productivity, and film thickness control.

The layer (cured resin layer) formed using the coating agent of the present invention exhibits excellent lamination (recoating) properties. 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 can be controlled to 30 to 50 mJ/ ^m² . Since many common solvents such as alcohols and ketones have a surface free energy similar to that of the cured resin layer, even a coating liquid using a common solvent can spread on the surface of the cured resin layer and laminate (recoat) the coating film without using special solvents with low surface free energy such as fluorine-based solvents.

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

The following monomers were used in the examples and comparative examples.

(However, Rf is given by either formula (1) or formula (2) below.)

(This represents a perfluoroalkyl group.)

[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.

[Preparation of the hardened film]
Coating method: Spin coating: 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.

[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 the diiodomethane contact angle to the Kaelble-Uy method.
○: Surface free energy value is within the range of 30 to 50 mJ/ ^m² ×: Surface free energy outside the above range ◆ Coatability (leveling properties)
The appearance of the hardened coating was visually inspected.
○: Good appearance ×: Poor appearance (uneven coating, paint defects, blemishes, etc.)

Example 1
(1) Synthesis of fluorine-containing copolymers 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 placed in a two-necked round-bottom flask, and 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.

After the reaction was complete, 4.00 g of propylene glycol monomethyl ether acetate was added to the reaction mixture until the solid content concentration reached 30%, yielding a fluorine-containing copolymer.

(2) Preparation of coating solution Coating solution 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 at 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 at a concentration of 1000 ppm as an active ingredient to prepare a thermosetting coating solution.

(3) Coating conditions: spin coat:
The coating solution was spin-coated onto a 4 cm square glass plate at a rotation speed of 1000 rpm for 10 seconds.

(4) Curing conditions UV light:
A cured film was obtained by exposure to a high-pressure mercury lamp at ^a pressure of 500 mJ/cm².
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.

(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.

Examples 1-50, Comparative Examples 1-12
Examples 1 to 50 exhibit good leveling and recoatability. Comparative Examples 1 to 4 and 7 to 10, which have a low fluorine content, show that the leveling properties are insufficient. Comparative Examples 5, 6, 11, and 12, which have a high proportion of fluorine monomer, show that they do not dissolve in the coating solution and remain on the coating film as foreign matter, reducing both leveling and recoatability.

Claims (8)

(i) Repeating units derived from monomer (A) and (ii) 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 , is a fluorine-containing copolymer:
(A) Fluorine-containing (meth)acrylate monomers represented by the following formula (I)
(In the formula, ^R1 represents a hydrogen atom or a methyl group. ^Y1 represents a divalent linking group. Rf is either formula (1) or formula (2) below.)
(This represents a perfluoroalkyl group represented by [the symbol].)
(B) (meth)acrylamide monomer represented by the following formula (II),
(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. ) (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)
(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).
(This represents a perfluoroalkyl group represented by [the symbol].)
(B) (meth)acrylamide monomer represented by the following formula (II),
(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.)
(C) A hydrophobic monomer represented by the following formula (III).
(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. 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. 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. A surface modifier comprising a fluorine-containing copolymer according to claim 1 or 2 . A leveling agent comprising a fluorine-containing copolymer according to claim 1 or 2 . 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 . An article comprising a layer formed using the coating agent described in claim 7.