Liquid repellent, liquid repellent composition, cured resin and article

Abstract

The present invention provides a liquid repellent that stably reduces surface free energy. A liquid repellent, which is composed of a carbamate reaction product formed by reacting a fluoropolymer containing a hydroxyl group and at least one (meth)acrylate monomer containing an isocyanate group, wherein the fluoropolymer containing a hydroxyl group is obtained by copolymerizing the following monomers (A) to (C): (A) at least one (meth)acrylate monomer containing a perfluoroether portion; (B) at least one (meth)acrylate monomer containing a hydroxyl group; (C) at least one (meth)acrylate monomer.

Description

Technical Field

[0001] The invention relates to a liquid repellent, a liquid repellent composition, a curing resin and an article. Background Art

[0002] In order to manufacture display pixels or wiring, color filters, biochips and other devices using printing technology represented by inkjet, it is required to pre-pattern the substrate in liquid-repellent areas and liquid-philic areas at the micron level using photolithography. In order to obtain the liquid-repellent area, a liquid-repellent agent is added to, for example, a UV-curable resin composition, a color photoresist, etc.

[0003] However, there is a problem that when a high-performance liquid repellent is added to a curable resin composition, a color resist, or the like, the color resist becomes cloudy or cavities are formed on the resist surface.

[0004] When the fluorinated 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 craters do not occur, but the liquid repellency is insufficient.

[0005] Prior art literature

[0006] Patent Literature

[0007] Patent Document 1: Japanese Patent No. 5997998 Summary of the invention

[0008] Problems to be solved by the invention

[0009] An object of the present invention is to provide a liquid repellent, a liquid repellent composition, a cured resin, and an article, which can stably reduce the surface free energy.

[0010] Technical solutions to solve problems

[0011] The present invention provides the following liquid repellent agent, liquid repellent composition, cured resin and article.

[0012] Item 1. A liquid repellent, comprising a urethane reaction product obtained by reacting a hydroxyl-containing fluorine-based polymer and at least one isocyanate-containing (meth)acrylate-based monomer, wherein the hydroxyl-containing fluorine-based polymer is obtained by copolymerizing the following monomers (A) to (C):

[0013] (A) at least one (meth)acrylate monomer containing a perfluoroether moiety;

[0014] (B) at least one hydroxyl-containing (meth)acrylate monomer;

[0015] (C) At least one (meth)acrylate monomer.

[0016] Item 2. The liquid repellent according to Item 1, wherein (A) comprises a (meth)acrylate monomer containing one perfluoroether moiety and a (meth)acrylate monomer containing a plurality of perfluoroether moieties.

[0017] Item 3. The liquid repellent according to Item 2, wherein the (meth)acrylate monomer containing one perfluoroether moiety is represented by the following formula (A1), and the (meth)acrylate monomer containing a plurality of perfluoroether moieties is represented by the following formula (A2),

[0018]

Chemical formula 1

[0019]

[0020] (Where R 1 It represents H or methyl.

[0021] R 2 It 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—), an ester bond (—COO— or —O—CO—), or an amide bond (—CONH— or —NHCO—) as required).

[0022] R 3 It represents H or methyl.

[0023] R 4 It 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—), an ester bond (—COO— or —O—CO—), or an amide bond (—CONH— or —NHCO—) as required).

[0024] n is an integer from 1 to 10. )

[0025] Item 4. The liquid repellent according to any one of Items 1 to 3, wherein the fluorine content of the hydroxyl group-containing fluorine-based polymer is 20 to 35% by mass.

[0026] Item 5. The liquid repellent according to any one of Items 1 to 4, wherein the liquid repellent is dissolved in a solvent.

[0027] Item 6. The liquid repellent according to any one of Items 1 to 5, wherein the liquid repellent is added to a UV curable resin for use.

[0028] Item 7. A liquid repellent composition comprising a UV curable resin and the liquid repellent agent according to any one of Items 1 to 5.

[0029] Item 8. A liquid repellent cured resin obtained by irradiating the liquid repellent composition according to Item 7 with ultraviolet rays.

[0030] Item 9. An article comprising the liquid repellent cured resin according to Item 8.

[0031] Effects of the Invention

[0032] By adding the liquid repellent of the present invention to a UV curable resin composition, a color resist, etc. and curing the resulting composition, a cured surface with greatly reduced free energy can be formed, and the free energy of the resulting cured surface changes little with time. DETAILED DESCRIPTION

[0033] When a composition obtained by adding the liquid repellent of the present invention to a UV curable resin or a color resist is applied on a substrate or the like and cured, liquid repellency can be imparted to the cured resin such as a cured film obtained by reacting the curing component contained in the UV curable resin or the color resist with the liquid repellent of the present invention.

[0034] ·Ingredients (A)

[0035] Examples of the perfluoroether portion of the (meth)acrylate monomer include -O-(perfluoroalkyl), -O-(perfluoroalkylene), and (perfluoroalkylene)-O-(perfluoroalkyl).

[0036] Specific examples of the perfluoroalkyl group include linear or branched C1-C8, preferably C1-C4, perfluoroalkyl groups such as -CF3, -CF2CF3, -CF2CF2CF3, -CF(CF3)2, and -CF2CF2CF2CF3.

[0037] Specific examples of the perfluoroalkylene group include linear or branched divalent C2-C8, preferably C2-C4, perfluoroalkylene groups such as -CF2-, -CF2CF2-, -CF(CF3)-, -CF2CF2CF2-, -CF2CF(CF3)-, -CF(CF3)CF2-, and -CF2CF2CF2CF3-.

[0038] The (meth)acrylate monomer containing a perfluoroether moiety is preferably represented by the following formula (A1) or (A2).

[0039]

Chemical formula 2

[0040]

[0041] (Where R 1 It represents H or methyl.

[0042] R 2It 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—), an ester bond (—COO— or —O—CO—), or an amide bond (—CONH— or —NHCO—) as required).

[0043] R 3 It represents H or methyl.

[0044] R 4 It 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—), an ester bond (—COO— or —O—CO—), or an amide bond (—CONH— or —NHCO—) as required).

[0045] n is an integer from 1 to 10. )

[0046] n is preferably 2-10, more preferably 3-9, further preferably 4-8, particularly preferably 5-7.

[0047] Examples of the divalent saturated aliphatic hydrocarbon group include C1 to C2-, -CH2CH2-, -CH(CH3)-, -CH2CH2CH2-, -CH2CH(CH3)-, -CH(CH3)CH2-, -CH2CH2CH2CH3- and the like. 10 , preferably a C1-C6, more preferably a C1-C4 divalent saturated aliphatic hydrocarbon group.

[0048] In addition, examples of divalent saturated aliphatic hydrocarbon groups having an ether bond include -CH2-O-CH2CH2-, -CH2CH2-O-CH2-, -(CH2CH2-O)1- (l is an integer of 1 to 5), etc. Examples of divalent saturated aliphatic hydrocarbon groups having an ester bond include -CH2CH2-COO-, -CH2CH2-OCO-, -CH2CH2CH2-COO-, -CH2CH2CH2-OCO-, -CH2CH2-COO-CH2-, -CH2CH2-OCO-CH2-, etc. Examples of divalent saturated aliphatic hydrocarbon groups having an amide bond include -CH2CH2-NHCO-, -CH2CH2-CONH-, -CH2-NHCO-CH2-, -CH2-CONH-CH2-, etc.

[0049] The (meth)acrylate monomer containing a perfluoroether moiety may be used alone or in combination of two or more.

[0050] Component (B)

[0051] The number of hydroxyl groups in the hydroxyl-containing (meth)acrylate monomer is 1 or 2, preferably 1. Preferred hydroxyl-containing (meth)acrylate monomers include compounds represented by the following formula (B1), and these may be used alone or in combination of two or more.

[0052]

Chemical formula 3

[0053]

[0054] (Where R 5 It represents H or methyl.

[0055] R 6 It represents an alkylene group having a straight chain or a branched chain.

[0056] m represents an integer from 1 to 20. )

[0057] Examples of the linear or branched alkylene group include C1 to C4 alkylene groups such as -CH2-, -CH2CH2-, -CH(CH3)-, -CH2CH2CH2-, -CH2CH(CH3)-, -CH(CH3)CH2-, and -CH2CH2CH2CH3-.

[0058] Component (C)

[0059] Examples of the (meth)acrylate monomer include methyl acrylate (MA), ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate (4-HBMA), isobutyl acrylate, sec-butyl acrylate, tert-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.

[0060] Hydroxyl-containing fluorinated polymers

[0061] The hydroxyl-containing fluorine-based polymer can be obtained by copolymerizing the above-mentioned component (A), component B, and component (C). The copolymerization reaction is advantageously carried out by reacting at 70 to 90° C. for 4 to 12 hours in the presence of a free radical initiator. Preferably, the polymerization is carried out in the presence of a free radical polymerization initiator as a free radical initiator. Examples of the radical polymerization initiator that can be used in the production method of the present invention include tert-butyl hydroperoxide, cumene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, diisopropylphenyl peroxide, di-tert-butyl peroxide, tert-butyl peroxyisobutyrate, tert-butyl-α-isopropylphenyl peroxide, di-α-isopropylphenyl peroxide, α,α′-bis(tert-butylperoxy)-p-diisopropylbenzene, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, 2,5-dimethyl-2,5-di(tert-butylperoxy)-hexyne-3-acetyl peroxide, succinic acid peroxide, diisobutyl peroxide, lauroyl peroxide, benzoyl peroxide, tert-butyl peroxide, Azo compounds such as oxyacetic acid ester, tert-butyl peroxyisobutyrate, di-isobutyl peroxydicarbonate, tert-butyl peroxyisopropyl carbonate, methyl ethyl ketone peroxide, cyclohexanone peroxide, 2,2'-azobisisobutyronitrile, 2,2'-azobisisobutyric acid dimethyl ester, azobisisobutyric acid dimethyl ester (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-methylamide oxime) dihydrochloride; potassium persulfate, sodium persulfate, ammonium persulfate, tert-butyl hydroperoxide, benzoyl peroxide, cumene hydroperoxide, etc. These free radical polymerization initiators may be used alone or in combination of two or more. In the copolymerization reaction, a chain transfer agent such as lauryl mercaptan, octyl mercaptan, dodecyl mercaptan, 2-mercaptoethanol, octyl thioglycolate, 3-mercaptopropionic acid, thioglycerol, etc. can be used to adjust the molecular weight.

[0062] The ratios of the component (A), the component (B), and the component (C) for obtaining the hydroxyl-containing fluorine-based polymer are as follows when the total is taken as 100 mass %.

[0063] Component (A): preferably 40 to 70% by mass, more preferably 50 to 60% by mass,

[0064] Component (B): preferably 10 to 40% by mass, more preferably 20 to 30% by mass,

[0065] Component (C): preferably 10 to 40% by mass, more preferably 20 to 30% by mass.

[0066] In the component (A) for obtaining the hydroxyl-containing fluorine-based polymer, the preferred mass ratio of the monomer represented by the formula (A1) to the monomer represented by the formula (A2) is monomer (A1): monomer (A2) = 1: 0 to 1: 0.4. If the amount of the component (A2) is too large relative to the component (A1), turbidity is generated in the liquid and the appearance of the liquid deteriorates.

[0067] The fluorine content of the hydroxyl-containing fluorine-based polymer is preferably 15 to 40% by mass, more preferably 20 to 35% by mass, and further preferably 22 to 32% by mass. If the fluorine content is too high, shrinkage cavities are generated on the surface of the cured resin obtained by mixing with the UV curable resin and curing, so it is not preferred. If the fluorine content is too low, liquid repellency is reduced, so it is not preferred.

[0068] The weight average molecular weight of the hydroxyl-containing fluorine-based polymer is preferably 3000 to 50000, more preferably 10000 to 20000. The weight average molecular weight can be calculated as a value converted into a molecular weight of standard polystyrene by gel permeation chromatography (GPC).

[0069] Isocyanate-containing (meth)acrylate monomers

[0070] Examples of the isocyanate group-containing (meth)acrylate monomer include 2-isocyanateethyl (meth)acrylate, 2-isocyanatepropyl (meth)acrylate, 3-isocyanatepropyl (meth)acrylate, 2-isocyanate-1-methylethyl (meth)acrylate, 2-isocyanate-1,1-dimethylethyl (meth)acrylate, 4-isocyanatecyclohexyl (meth)acrylate, 2-(2-(meth)acryloyloxyethyloxy)ethyl isocyanate, 1,1-(bis(meth)acryloyloxymethyl)ethyl isocyanate, 2-(2-(meth)acryloyloxyethyloxy)ethyl isocyanate, 1,1-(bis(meth)acryloyloxymethyl)ethyl isocyanate, 2-(2-isocyanatoethoxy)ethyl (meth)acrylate, and 2-(2-isocyanatoethoxy) (meth)acrylate. 2-isocyanateethyl (meth)acrylate is preferred. The isocyanate group-containing (meth)acrylate monomer may be used alone or in combination of two or more.

[0071] ·Carbamate reaction products

[0072] The carbamate reaction product can be obtained by reacting a hydroxyl-containing fluoropolymer and an isocyanate-containing (meth)acrylate monomer in the presence of an amine catalyst as required. Examples of the amine catalyst include triethylamine, N-methylmorpholine, N-ethylmorpholine, N,N'-dimethylpiperazine, benzyldimethylamine, N,N-dimethylethanolamine, bis(dimethylaminoethyl)ether, and the like. The reaction is advantageously carried out by using 0.3 to 1.0 equivalents of an isocyanate-containing (meth)acrylate monomer relative to 1 equivalent of hydroxyl groups in the hydroxyl-containing fluoropolymer and reacting at 50 to 80°C for 4 to 8 hours.

[0073] Liquid repellent, liquid repellent composition, liquid repellent curing resin, article

[0074] The liquid repellent of the present invention preferably contains a carbamate reaction product and further contains a liquid repellent of a solvent. As the solvent, there can be mentioned: 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 , propylene glycol monomethyl ether acetate (PGMEA), 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-butanediol 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, 1,4-dioxane, etc.

[0075] The liquid repellent of the present invention can be made into a liquid repellent composition by adding it to a UV curable resin. The UV curable resin and the liquid repellent composition are preferably liquid substances. By curing the liquid repellent composition, liquid repellency can be imparted to the cured resin. Since the carbamate-based reaction product of the present invention can be added to the UV curable resin to impart liquid repellency to its cured product, it is useful as a liquid repellent additive for UV curable resins.

[0076] The liquid repellent of the present invention is a liquid repellent having a continuous liquid repellent performance. For example, when the liquid repellent composition is prepared by mixing with a curable resin, and the liquid repellent composition is cured to obtain a cured resin (cured film), the absolute value of the rate of change of the initial surface free energy (SFE0) of the cured resin and the surface energy (SFE3) after 3 days (expressed by formula X) is 10% or less, preferably 5% or less, more preferably 4% or less, and particularly 3% or less.

[0077]

Mathematical formula 1

[0078] |(100×(SFE3-SFE0) / SFE0| Formula X

[0079] As UV curable resin, acrylic resin, epoxy resin, melamine resin etc. can be used. The UV curable resin of a preferred embodiment is used for the manufacture of color filter, color photoresist etc. Color photoresist comprises the photoresist (black photoresist) used for black matrix manufacturing. In order to meet the physical properties such as heat resistance, hot water resistance, chemical resistance, UV curable resin can be a curable resin with more than 2 functions. In order to obtain low viscosity, liquid repellent composition, UV curable resin preferably shows low molecular weight, amorphous resin.

[0080] Taking the total solid content as 100 mass %, the liquid repellent composition of the present invention preferably contains 20 to 40 mass % of a UV curable resin (solid content) and 0.05 to 2.0 mass % of a liquid repellent solid content, and more preferably contains 25 to 35 mass % of a UV curable resin (solid content) and 0.2 to 0.7 mass % of a liquid repellent solid content.

[0081] Liquid repellent cured resin can be obtained by curing the liquid repellent composition of the present invention by UV (ultraviolet) irradiation. Curing can be implemented under the curing conditions of UV curing resin. In a preferred embodiment, by applying the liquid repellent composition of the present invention to a substrate and UV curing, an article having a cured film as a cured resin can be obtained. The cured film has a liquid repellent surface. As a substrate, silicon wafers, synthetic resins, glass, metals, ceramics, etc. can be cited. The synthetic resin can be any one of thermoplastic resins and thermosetting resins. As glass, for example, silicate glass, alkali silicate glass, soda lime glass, potassium lime glass, lead glass, barium glass, borosilicate glass, etc. can be cited. As metals, gold, silver, copper, iron, nickel, aluminum, platinum, etc. can be cited. As ceramics, oxides (such as aluminum oxide, zinc oxide, titanium oxide, silicon oxide, zirconium oxide, barium titanate), nitrides (such as silicon nitride, boron nitride), sulfides (such as cadmium sulfide), carbides (such as silicon carbide), etc.

[0082] The coating of the liquid repellent composition on the substrate can be carried out by, for example, roll coating, gravure coating, micro gravure coating, flow coating, rod coating, spray coating, die coating, spin coating, dip coating, etc., and can be selected in consideration of the type, shape, productivity, controllability of film thickness, etc. of the substrate.

[0083] [Example]

[0084] Hereinafter, the present invention will be described in detail with reference to examples.

[0085] Materials used

[0086] AC-500: 2-Propenoic acid, 2-methyl-, 2-[2,3,3,3-tetrafluoro-2-(1,1,2,2,3,3,3-heptafluoropropoxy)-1-oxopropoxy]ethyl ester

[0087]

Chemical formula 4

[0088]

[0089] AC-1000: Poly[oxy[trifluoro(trifluoromethyl)-1,2-ethanediyl]], α-(1,1,2,2,3,3,3-heptafluoropropyl)-ω-[1,2,2,2-tetrafluoro-1-[[2-[(2-methyl-1-oxo-2-propen-1-yl)oxy]ethoxy]carbonyl]ethoxy]-

[0090]

Chemical formula 5

[0091]

[0092] PE-90: Poly(oxy-1,2-ethanediyl),α-(2-methyl-1-oxo-2-propen-1-yl)-ω-hydroxy-

[0093]

Chemical formula 6

[0094]

[0095] 4-HBMA: 2-Propenoic acid, 2-methyl-, 4-hydroxybutyl ester

[0096]

Chemical formula 7

[0097]

[0098] MMA: 2-Propenoic acid, 2-methyl-, methyl ester

[0099]

Chemical formula 8

[0100]

[0101] PME-200: Poly(oxy-1,2-ethanediyl),α-(2-methyl-1-oxo-2-propen-1-yl)-ω-methoxy-

[0102]

Chemical formula 9

[0103]

[0104] CALENDS AOI: 2-Isocyanatoethyl acrylate

[0105]

Chemical formula 10

[0106]

[0107] FTERGENT 601ADH2: (manufactured by Neos Co., Ltd.)

[0108] Synthesis example 1

[0109] AC-500 (50 g), PE-90 (20 g), MMA (20 g), butyl acetate (200 g), lauryl mercaptan (1.48 g), and V-601 (0.84 g) were added to a three-necked flask (500 ml) with a cooling tube. Nitrogen gas was introduced into the reaction solution to replace the reaction container with nitrogen. After nitrogen replacement, the reaction solution was heated to 80°C while stirring to start the reaction. Thereafter, stirring was continued at 80°C for 8 hours. 1 The end of the reaction was confirmed by the disappearance of the peaks specific to each acrylate in H-NMR. The target fluorinated oligomer was obtained quantitatively. 50 mol% of CALENDS AOI and 1 mol% of triethylamine were added to PE-90, and the reaction solution was stirred continuously at 50°C for 8 hours. Using FT-IR, the end of the reaction was confirmed by the disappearance of -N=C=O absorption. The reactive fluorinated oligomer 1 as the target carbamate reaction product was obtained quantitatively.

[0110] Synthesis Examples 2 to 9

[0111] Reactive fluorinated oligomers 2 to 9 were synthesized by carrying out the same operation as in Synthesis Example 1 except that the monomer weights were as shown in Table 1.

[0112] Synthesis example 10

[0113] FTERGENT 601ADH2 was set as the reactive fluorinated oligomer 10 .

[0114]

Table 1

[0115]

[0116] Examples 1 to 5 and Comparative Examples 1 to 5

[0117] The reactive fluorinated oligomers 1 to 9 synthesized in Synthesis Examples 1 to 9 were added so that the concentration of the active ingredient of the liquid repellent agent was 0.5 wt % relative to the active ingredient of the photoresist coating solution. The coating solution was applied to a glass substrate by spin coating, and after heating and drying, a coating film was prepared by UV irradiation, and the following evaluation was performed. The results are shown in Table 2.

[0118] Examples 6 to 10 and Comparative Examples 6 to 9

[0119] Reactive fluorinated oligomers 1 to 9 synthesized in Synthesis Examples 1 to 9 were added so that the concentration of the active ingredient of the liquid repellent agent was 0.5 wt % relative to the active ingredient of the UV curing bar coating liquid containing dipentaerythritol hexaacrylate. The bar coating liquid was applied to a PET substrate by bar coating, and after heating and drying, a coating film was prepared by UV irradiation, and the following evaluation was performed. The results are shown in Table 3.

[0120] evaluate

[0121] Film appearance

[0122] The film appearance of each coating film was visually observed, and a case where there was no shrinkage cavity on the film was rated as 0, and a case where there was shrinkage cavity or the like in appearance was rated as x.

[0123] Surface free energy determination

[0124] The contact angle of the produced coating film was measured to calculate the surface free energy. The Kaelble-Uy formula was used as the calculation formula.

[0125] If the initial surface free E is 17 mN / m or less, the performance is good.

[0126] Membrane performance stability

[0127] The produced coating film was stored in an environment of 25° C. and 30% for 3 days. The contact angle after storage was measured, and the surface free E was calculated.

[0128] The initial and after preservation surface free energies were compared.

[0129] If the change in surface free E after 3 days is less than 1 mN / m, it is considered to be 0.

[0130] If the amount of change in surface free energy E after 3 days is 1 mN / m or more, it is rated as ×.

[0131]

Table 2

[0132]

[0133]

Table 3

[0134]

[0135] As shown in Table 2, it can be seen that the FTERGENT 601ADH2 used in Comparative Example 5 not only has a high initial SFE, but also changes by more than 10% after 3 days relative to the initial SFE, which is not preferred. The liquid repellent of the present invention has a very low initial SFE, and the rate of change of SFE after 3 days relative to the initial SFE is less than 5%, which is preferred as a liquid repellent for imparting liquid repellency to a coating material for a photoresist.

[0136] As shown in Table 3, in the case of UV curing bar coating, Examples 6 to 10 had good film appearance and good initial SFE. In the case of Comparative Examples 6 to 9, shrinkage holes were generated in the film appearance. It can be seen that the liquid repellent of the present invention is preferred as a liquid repellent for imparting liquid repellency to the UV curing bar coating.

Claims

1. A liquid repellent, comprising a carbamate reaction product obtained by reacting a hydroxyl-containing fluorine-based polymer and at least one isocyanate-containing (meth)acrylate-based monomer, wherein the hydroxyl-containing fluorine-based polymer is obtained by copolymerizing the following monomers (A) to (C), The monomer (A) is a (meth)acrylate monomer containing a perfluoroether moiety and comprising at least one selected from the group consisting of a monomer represented by the following formula (A1) and a monomer represented by the following formula (A2), ; In formula (A1), R 1 represents H or methyl, R 2 represents a divalent saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms; the saturated aliphatic hydrocarbon group is a straight chain type or a branched chain type, and is a saturated aliphatic hydrocarbon group, a saturated aliphatic hydrocarbon group having an ether bond, a saturated aliphatic hydrocarbon group having an ester bond, or a saturated aliphatic hydrocarbon group having an amide bond, In formula (A2), R 3 represents H or methyl, R 4 represents a divalent saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms; the saturated aliphatic hydrocarbon group is a straight chain type or a branched chain type, and is a saturated aliphatic hydrocarbon group, a saturated aliphatic hydrocarbon group having an ether bond, a saturated aliphatic hydrocarbon group having an ester bond, or a saturated aliphatic hydrocarbon group having an amide bond, n is an integer from 1 to 10; The monomer (B) is at least one hydroxyl-containing (meth)acrylate monomer including a monomer represented by the following formula (B1), ; In formula (B1), R 5 represents H or methyl, R 6 represents a linear or branched alkylene group, m represents an integer from 1 to 20; The monomer (C) is at least one (meth)acrylate monomer selected from the group consisting of methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, tert-butyl acrylate, pentyl acrylate, hexyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, phenyl acrylate, benzyl acrylate, methyl methacrylate, 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, When the total amount of the monomer (A), the monomer (B) and the monomer (C) is taken as 100% by mass, The monomer (A) is 40 to 60% by mass, and the mass ratio of the monomer (A1) to the monomer (A2) is 1:0 to 1:0.4, The monomer (B) is 10% to 40% by mass. The monomer (C) is 10 to 40% by mass.

2. The liquid repellent according to claim 1, wherein The urethane reaction product is obtained by reacting 0.3 to 1.0 equivalent of an isocyanate group-containing (meth)acrylate monomer with respect to 1 equivalent of the hydroxyl group of the fluoropolymer containing a hydroxyl group.

3. The liquid repellent according to claim 1, wherein The fluorine content of the hydroxyl-containing fluorine-based polymer is 20 to 35% by mass.

4. The liquid repellent according to claim 1, wherein The liquid repellent is dissolved in a solvent.

5. The liquid repellent according to claim 1, wherein The liquid repellent is added to the UV curing resin for use. 6 . A liquid repellent composition comprising a UV curable resin and the liquid repellent agent according to claim 1 . 7 . A liquid repellent cured resin obtained by irradiating the liquid repellent composition according to claim 6 with ultraviolet rays. 8 . An article comprising the liquid repellent cured resin according to claim 7 .

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