Liquid repellent additives

Abstract

To provide a liquid repellent additive capable of imparting good liquid repellency to an ultraviolet curable composition containing inorganic particles.SOLUTION: There is provided a liquid repellent additive containing an ester-based reaction product of a hydroxyl group-containing fluorinated polymer (A) and at least one (meth)acrylate-based monomer (B) selected from the group consisting of a carboxylic acid halide having a (meth)acrylate group, a carboxylic acid anhydride having a (meth)acrylate group and a carboxylic acid having a (meth)acrylate group, wherein the reaction ratio between the hydroxyl groups in the hydroxyl group-containing fluorinated polymer (A) and the (meth)acrylate-based monomer (B) is 1:1.0 to 1:1.5 by a molar ratio and the hydroxyl group-containing fluorinated polymer (A) is obtained by copolymerization of the following (a) to (C): (a) at least one (meth)acrylate monomer containing a perfluoroether moiety, (b) at least one hydroxyl group-containing (meth)acrylate-based monomer and (c) at least one (meth)acrylate-based monomer.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a liquid repellent additive. [Background technology]

[0002] A known technique for imparting liquid repellency to an ultraviolet-cured coating film is to add a liquid-repellent additive consisting of a fluorine-containing oligomer to the ultraviolet-cured coating material (Patent Documents 1 and 2). The fluorine-containing oligomers described in Patent Documents 1 and 2 have UV-reactive groups in their structure, and therefore chemically bond to the ultraviolet-cured coating film, resulting in excellent durability of the coating film's liquid repellency. Patent Documents 1 and 2 use a urethanization reaction using an isocyanate having a UV-reactive group as a method for introducing the UV-reactive group into the structure of the fluorine-containing oligomer.

[0003] On the other hand, a technique is known in which inorganic particles such as colloidal silica or hollow silica are blended into an ultraviolet-curable coating material in order to impart scratch resistance and lower the refractive index of the ultraviolet-curable coating film (Patent Document 3).

[0004] However, when a liquid-repellent additive consisting of a fluorine-containing oligomer having a urethane structure as described in Patent Documents 1 and 2 is used for an ultraviolet-curable paint containing inorganic particles, the urethane structure in the fluorine-containing oligomer structure interacts with the inorganic particles, causing the inorganic particles to aggregate, making it difficult to apply the liquid-repellent additive to an ultraviolet-curable paint containing inorganic particles. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Patent No. 5997998 [Patent Document 2] Japanese Patent Publication No. 2020-032658 [Patent Document 3] Japanese Patent Application Laid-Open No. 61-181809 Summary of the Invention [Problem to be solved by the invention]

[0006] An object of the present invention is to provide a liquid-repellent additive that can impart good liquid repellency not only to ultraviolet-curable compositions that do not contain inorganic particles, but also to ultraviolet-curable compositions that contain inorganic particles. [Means for solving the problem]

[0007] In order to solve the above problems, the present inventors have conducted extensive research and have found that the aggregation of inorganic particles can be suppressed by using a fluorine-containing oligomer having an ester structure.

[0008] The present invention has been completed based on these findings and includes the following broad aspects. [Section 1] a hydroxyl group-containing fluorine-based polymer (A); A liquid repellent additive comprising an ester-based reaction product with at least one (meth)acrylate monomer (B) selected from the group consisting of a carboxylic acid halide having a (meth)acrylate group, a carboxylic acid anhydride having a (meth)acrylate group, and a carboxylic acid having a (meth)acrylate group, the reaction ratio of the hydroxyl groups in the hydroxyl group-containing fluorine-based polymer (A) to the (meth)acrylate-based monomer (B) is 1:1.0 to 1:1.5 in terms of molar ratio; The hydroxyl group-containing fluorine-based polymer (A) is selected from the following (a) to (c): (a) at least one (meth)acrylate monomer containing a perfluoroether moiety; (b) at least one hydroxyl group-containing (meth)acrylate monomer (c) at least one (meth)acrylate monomer A liquid-repellent additive obtained by copolymerizing a monomer of the formula (I). [Section 2] Item 2. The liquid repellent additive according to Item 1, wherein the monomer (a) comprises a (meth)acrylate monomer containing one perfluoroether moiety and a (meth)acrylate monomer containing multiple perfluoroether moieties. [Section 3] Item 3. The liquid repellent additive 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):

[0009] [ka]

[0010] (In the formula, R 1 represents a hydrogen atom 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 optionally have an ether bond (-O-), an ester bond (-COO- or -O-CO-), or an amide bond (-CONH- or -NHCO-)). R 3 represents a hydrogen atom or a methyl group. R 4 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 optionally have an ether bond (-O-), an ester bond (-COO- or -O-CO-), or an amide bond (-CONH- or -NHCO-)). n is an integer from 1 to 10. [Section 4] 4. The liquid-repellent additive according to any one of items 1 to 3, wherein the fluorine content of the hydroxyl group-containing fluorine-based polymer (A) is 20 to 35% by mass. [Section 5] Item 5. The liquid repellent additive according to any one of items 1 to 4, wherein the (meth)acrylate monomer (B) is a carboxylic acid halide having a (meth)acrylate group. [Section 6] Item 6. The liquid-repellent additive according to any one of items 1 to 5, which is dissolved in a solvent. [Section 7] Item 7. The liquid-repellent additive according to any one of items 1 to 6, which is used by being added to a UV-curable resin. [Section 8] Item 8. A liquid-repellent composition comprising a UV-curable resin and the liquid-repellent additive according to any one of Items 1 to 7. [Section 9] Item 9. A liquid-repellent cured resin obtained by irradiating the liquid-repellent composition according to item 8 with ultraviolet light. [Section 10] Item 10. An article comprising the liquid-repellent cured resin according to item 9. [Effects of the Invention]

[0011] According to the present invention, it is possible to provide a liquid-repellent additive that can impart good liquid repellency to ultraviolet-curable paints that contain inorganic particles. DETAILED DESCRIPTION OF THE INVENTION

[0012] The liquid repellent additive of the present invention is a hydroxyl group-containing fluorine-based polymer (A); (B) at least one (meth)acrylate-based monomer selected from the group consisting of carboxylic acid halides having a (meth)acrylate group, carboxylic acid anhydrides having a (meth)acrylate group, and carboxylic acids having a (meth)acrylate group; Includes ester-based reaction products with

[0013] <Hydroxyl group-containing fluoropolymer (A)> The hydroxyl group-containing fluorine-based polymer (A) is a polymer obtained by copolymerizing the following monomers (a) to (c). (a) at least one (meth)acrylate monomer containing a perfluoroether moiety; (b) at least one hydroxyl group-containing (meth)acrylate monomer (c) at least one (meth)acrylate monomer

[0014] (a) At least one (meth)acrylate monomer containing a perfluoroether moiety The perfluoroether moiety in the monomer (a) is -O-(perfluoroalkyl group), -O-(perfluoroalkylene group), (perfluoroalkylene group)-O-(perfluoroalkyl group), Examples include:

[0015] Specific examples of the perfluoroalkyl group include linear or branched C1 to C8, preferably C1 to C4, perfluoroalkyl groups such as -CF3, -CF2CF3, -CF2CF2CF3, -CF(CF3)2, and -CF2CF2CF2CF3.

[0016] 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-.

[0017] The monomer (a) is preferably a monomer represented by the following formula (a1) or (a2).

[0018] [ka]

[0019] (In the formula, R 1 represents a hydrogen atom 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 optionally have an ether bond (-O-), an ester bond (-COO- or -O-CO-), or an amide bond (-CONH- or -NHCO-)). R 3 represents a hydrogen atom or a methyl group. R 4represents a divalent saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms (the saturated aliphatic hydrocarbon group may be linear or branched, and may optionally have an ether bond (-O-), an ester bond (-COO- or -O-CO-), or an amide bond (-CONH- or -NHCO-)). n is an integer from 1 to 10.

[0020] R 1 represents a hydrogen atom or a methyl group, and is preferably a methyl group.

[0021] 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 optionally have an ether bond (-O-), an ester bond (-COO- or -O-CO-), or an amide bond (-CONH- or -NHCO-).

[0022] Examples of the divalent saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms include C1 to C6 groups such as -CH2-, -CH2CH2-, -CH(CH3)-, -CH2CH2CH2-, -CH2CH(CH3)-, -CH(CH3)CH2-, and -CH2CH2CH2CH3-. 10 Preferably, the alkyl group is a C1 to C6, more preferably a C1 to C4 divalent saturated aliphatic hydrocarbon group.

[0023] Examples of the divalent saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms and an ether bond include -CH2-O-CH2CH2-, -CH2CH2-O-CH2-, -(CH2CH2-O) l - (l is an integer of 1 to 5), etc.

[0024] Examples of the divalent saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms and an ester bond include -CH2CH2-COO-, -CH2CH2-OCO-, -CH2CH2CH2-COO-, -CH2CH2CH2-OCO-, -CH2CH2-COO-CH2-, and -CH2CH2-OCO-CH2-.

[0025] Examples of the divalent saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms and an amide bond include -CH2CH2-NHCO-, -CH2CH2-CONH-, -CH2-NHCO-CH2-, and -CH2-CONH-CH2-.

[0026] R 3 represents a hydrogen atom or a methyl group, and is preferably a methyl group.

[0027] R 4 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 optionally have an ether bond (-O-), an ester bond (-COO- or -O-CO-), or an amide bond (-CONH- or -NHCO-).

[0028] Examples of the divalent saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms include C1 to C6 groups such as -CH2-, -CH2CH2-, -CH(CH3)-, -CH2CH2CH2-, -CH2CH(CH3)-, -CH(CH3)CH2-, and -CH2CH2CH2CH3-. 10 Preferably, the alkyl group is a C1 to C6, more preferably a C1 to C4 divalent saturated aliphatic hydrocarbon group.

[0029] Examples of the divalent saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms and an ether bond include -CH2-O-CH2CH2-, -CH2CH2-O-CH2-, -(CH2CH2-O) l - (l is an integer of 1 to 5), etc.

[0030] Examples of the divalent saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms and an ester bond include -CH2CH2-COO-, -CH2CH2-OCO-, -CH2CH2CH2-COO-, -CH2CH2CH2-OCO-, -CH2CH2-COO-CH2-, and -CH2CH2-OCO-CH2-.

[0031] Examples of the divalent saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms and an amide bond include -CH2CH2-NHCO-, -CH2CH2-CONH-, -CH2-NHCO-CH2-, and -CH2-CONH-CH2-.

[0032] n is an integer of 1 to 10, preferably 2 to 10, more preferably 3 to 9, even more preferably 4 to 8, and particularly preferably 5 to 7.

[0033] Monomer (a) is commercially available or can be produced by known methods, such as AC-500, AC-600, and AC-1000 (all manufactured by Shinochem).

[0034] The monomer (a) may be used alone or in combination of two or more kinds.

[0035] (b) At least one hydroxyl group-containing (meth)acrylate monomer The number of hydroxyl groups in the monomer (b) is one or two, and preferably one. The monomer (b) is preferably a monomer represented by the following formula (b1):

[0036] [ka]

[0037] (In the formula, R 5 indicates H or a methyl group. R 6 represents a linear or branched alkylene group. m represents an integer of 1 to 20.

[0038] R 5 represents H or a methyl group, and is preferably a methyl group.

[0039] R 6represents a linear or branched alkylene group, preferably a linear or branched alkylene group having 1 to 6 carbon atoms, and more preferably a linear or branched alkylene group having 1 to 4 carbon atoms.

[0040] 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-.

[0041] m is an integer of 1 to 20, preferably 1 to 10, and more preferably 1 to 4.

[0042] Monomer (b) is commercially available or can be produced by a known method. Examples of commercially available products include Blemmer E, Blemmer PE-90, Blemmer PE-200, Blemmer PE-350, Blemmer P, Blemmer PP-1000, Blemmer PP-500, and Blemmer PP-800 (all manufactured by NOF Corporation), Light Ester HO-250(N), Light Ester HOP(N), Light Ester HOA(N), Light Ester HOP-A(N), and Light Ester HOB(N) (all manufactured by Kyoeisha Chemical Co., Ltd.).

[0043] The monomer (b) may be used alone or in combination of two or more kinds.

[0044] (c) At least one (meth)acrylate monomer Examples of the (meth)acrylate monomer include methyl acrylate (MA), ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, 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.

[0045] (Method for producing hydroxyl group-containing fluorine-based polymer (A)) The hydroxyl group-containing fluorine-based polymer can be obtained by copolymerizing the above-mentioned monomers (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.

[0046] As for the radical initiator, it is preferable to carry out polymerization in the presence of a radical polymerization initiator. Examples of the radical polymerization initiator 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, t-butyl peroxyisobutyrate, diisobutyl Examples of suitable azo compounds include peroxydicarbonate, t-butylperoxyisopropyl carbonate, methyl ethyl ketone peroxide, cyclohexanone peroxide, 2,2'-azobisisobutyronitrile, dimethyl 2,2'-azobisisobutyrate, dimethyl azobisisobutyrate (V-601, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 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-methylamidoxime) dihydrochloride; potassium persulfate, sodium persulfate, ammonium persulfate, potassium persulfate, t-butyl hydroperoxide, benzoyl peroxide, and cumene hydroperoxide. These radical polymerization initiators may be used alone or in combination of two or more. In the copolymerization reaction, the molecular weight 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.

[0047] The proportions of the monomers (a), (b), and (c) used to obtain the hydroxyl group-containing fluoropolymer are expressed as follows, with the total of these being 100% by mass: Monomer (a): preferably 40 to 70 mass%, more preferably 50 to 60 mass%, Monomer (b): preferably 10 to 40 mass%, more preferably 20 to 30 mass%, Monomer (c): preferably 10 to 40 mass%, more preferably 20 to 30 mass%, is.

[0048] In the monomer (a) used to obtain the hydroxyl group-containing fluorine-based polymer (A), the mass ratio of the monomer represented by formula (a1) to the monomer represented by formula (a2) is preferably monomer (a1):monomer (a2)=1:0 to 1:0.4. When the amount of monomer (a2) relative to monomer (a1) is 0.4 or less, the liquid is less likely to become cloudy and the appearance is less likely to be poor, which is preferable.

[0049] The fluorine content of the hydroxyl group-containing fluorine-based polymer (A) is preferably 15 to 40% by mass, more preferably 20 to 35% by mass, and even more preferably 22 to 32% by mass. A fluorine content of 15% by mass or more is preferred because it improves liquid repellency. A fluorine content of 40% by mass or less is preferred because it is less likely to cause cissing on the surface of the cured resin obtained by mixing with a UV-curable resin and curing it.

[0050] The weight average molecular weight of the hydroxyl group-containing fluorine-based polymer (A) is preferably 3,000 to 100,000, more preferably 20,000 to 40,000. The weight average molecular weight can be calculated by gel permeation chromatography (GPC) as a value converted into the molecular weight of standard polystyrene.

[0051] <(Meth)acrylate Monomer (B)> The (meth)acrylate monomer (B) is at least one (meth)acrylate monomer selected from the group consisting of a carboxylic acid halide having a (meth)acrylate group, a carboxylic acid anhydride having a (meth)acrylate group, and a carboxylic acid having a (meth)acrylate group.

[0052] Examples of the halogen atom of the carboxylic acid halide having a (meth)acrylate group include fluoride, chloride, bromide, and iodide. Examples of the carboxylic acid halide having a (meth)acrylate group include acryloyl chloride, methacryloyl chloride, acryloyl bromide, methacryloyl bromide, acryloyl iodide, methacryloyl iodide, acryloyl fluoride, and methacryloyl fluoride.

[0053] Examples of carboxylic acid anhydrides having a (meth)acrylate group include acrylic acid anhydride and methacrylic acid anhydride.

[0054] Examples of carboxylic acids having a (meth)acrylate group include acrylic acid and methacrylic acid.

[0055] Among these, from the viewpoint of ease of purification after the esterification reaction of the hydroxyl group-containing fluorine-based polymer (A) and the (meth)acrylate-based monomer (B), it is preferable to use a carboxylic acid halide having a (meth)acrylate group as the (meth)acrylate-based monomer (B).

[0056] The (meth)acrylate monomer (B) may be used alone or in combination of two or more kinds.

[0057] <Ester reaction products> The ester-based reaction product can be obtained by reacting a hydroxyl group-containing fluoropolymer (A) with a (meth)acrylate monomer (B) such that the molar ratio of the hydroxyl groups in the hydroxyl group-containing fluoropolymer (A) to the (meth)acrylate monomer (B) is 1:1.0 to 1:1.5, preferably 1:1.0 to 1:1.2. The reaction is carried out, if necessary, in the presence of a base. Examples of the base include organic bases such as triethylamine, tributylamine, pyridine, 4-dimethylaminopyridine, diazabicyclononene, and diazabicycloundecene; inorganic bases such as sodium hydride, potassium hydride, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, and cesium carbonate; alkali metal alkoxides such as sodium methoxide, sodium ethoxide, and potassium tert-butoxide; and organic lithium compounds such as methyllithium and butyllithium. The reaction may also be carried out using a condensing agent or catalyst, if necessary.

[0058] Relative to 1 equivalent of hydroxyl groups in the hydroxyl group-containing fluoropolymer (A), 1.0 to 1.5 equivalents, preferably 1.0 to 1.2 equivalents, of the (meth)acrylate monomer (B) are used, and the reaction is carried out at 25 to 80°C for 1 to 48 hours. Preferably, 95% or more (more preferably 97% or more, even more preferably 98% or more, particularly preferably 99% or more, and most preferably 100%) of the hydroxyl groups in the hydroxyl group-containing fluoropolymer (A) are reacted with the (meth)acrylate monomer (B) and esterified. Because hydroxyl groups have the ability to adsorb to inorganic particles, it is preferable that 95% or more of the hydroxyl groups are esterified, as this inhibits aggregation of the inorganic particles.

[0059] The weight-average molecular weight of the ester-based reaction product is preferably 3,000 to 100,000, and more preferably 20,000 to 40,000. The weight-average molecular weight can be calculated by gel permeation chromatography (GPC) as a value converted into the molecular weight of standard polystyrene.

[0060] <Liquid-repellent additive, liquid-repellent composition, liquid-repellent cured resin, and article> The liquid-repellent additive of the present invention is preferably a liquid liquid-repellent additive that contains an ester-based reaction product and further contains a solvent. The solvent is not particularly limited as long as it is capable of dissolving the ester-based reaction product, and examples thereof 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 ... Examples of solvents that can be used include methylcellulose, methylcellulose dimethicone, methylcellulose 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-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.

[0061] The liquid-repellent additive of the present invention may be appropriately blended with rust inhibitors, catalysts, antibacterial agents, flame retardants, antifoaming agents, thickeners, viscosity modifiers, leveling agents, ultraviolet absorbers, preservatives, antifreeze agents, wetting agents, pH adjusters, stabilizers, antifungal agents, light-resistant stabilizers, weather-resistant stabilizers, neutralizing agents, matting agents, drying accelerators, foaming agents, non-stick agents, anti-deterioration agents, and the like, within the scope that does not impair the object of the present invention.

[0062] The liquid-repellent additive of the present invention can be added to a UV-curable resin to form a liquid-repellent composition. The UV-curable 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 ester-based reaction product of the present invention can be added to a UV-curable resin to impart liquid repellency to the cured product, making it useful as a liquid-repellent additive for UV-curable resins.

[0063] The liquid-repellent additive of the present invention can also be used for UV-curable resins containing inorganic particles. The liquid-repellent additive of the present invention does not have a urethane structure or a hydroxyl group, which are functional groups that are highly adsorbent to inorganic particles, and has low adsorption to inorganic particles. Therefore, even when added to a UV-curable resin containing inorganic particles, aggregation of the inorganic particles is suppressed and the dispersibility of the inorganic particles in the UV-curable resin is not impaired.

[0064] As the inorganic particles, for example, inorganic particles having an average primary particle size of 5 nm or more and 100 nm or less can be used.

[0065] Preferred examples of inorganic particles include silica (colloidal silica, hollow silica, fumed silica, precipitated silica, etc.), alumina, zirconia, titania, and metal oxide particles such as zinc oxide.

[0066] The content of inorganic particles in the UV curable resin is not particularly limited, and can be, for example, 1 to 20% by mass, and preferably 2 to 15% by mass.

[0067] Examples of UV-curable resins that can be used include acrylic resins, epoxy resins, and melamine resins. The UV-curable resin may be a bifunctional or higher curable resin in order to satisfy physical properties such as heat resistance, hot water resistance, and chemical resistance. UV-curable resins that are low in molecular weight and amorphous are preferred in order to obtain a low-viscosity, liquid-state liquid-repellent composition.

[0068] The liquid-repellent composition of the present invention preferably contains 20 to 40 mass% of UV-curable resin (solid content) and 0.05 to 2.0 mass% of the solid content of the liquid-repellent additive, and more preferably contains 25 to 35 mass% of UV-curable resin (solid content) and 0.2 to 0.7 mass% of the solid content of the liquid-repellent additive, with the total solid content being 100 mass%.

[0069] A liquid-repellent cured resin can be obtained by curing the liquid-repellent composition of the present invention by UV (ultraviolet) irradiation. Curing can be carried out under the curing conditions for UV-curable resins. In a preferred embodiment, an article having a cured film as a cured resin can be obtained by applying the liquid liquid-repellent composition of the present invention to a substrate and curing it with UV. This cured film has a liquid-repellent surface. Examples of substrates include silicon wafers, synthetic resins, glass, metals, and ceramics.

[0070] 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, and barium titanate), nitrides (e.g., silicon nitride and boron nitride), sulfides (e.g., cadmium sulfide), and carbides (e.g., silicon carbide).

[0071] 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 taking into consideration the type, shape, productivity, controllability of film thickness, and the like of the substrate. [Example]

[0072] The present invention will be further explained below with reference to examples, but the present invention is not limited thereto.

[0073] <Materials used> AC-600: 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]-

[0074] [ka]

[0075] (n=1(average)) MMA: Methyl methacrylate PE-90: Poly(oxy-1,2-ethanediyl), α-(2-methyl-1-oxo-2-propen-1-yl)-ω-hydroxy-

[0076] [ka]

[0077] (m=2(average)) Acryl-Cl: Acryloyl chloride AOI: 2-isocyanatoethyl acrylate, Karenz AOI (Showa Denko K.K.) Futergent 601ADH2: Liquid repellent with a urethane structure and hydroxyl groups (manufactured by Neos Co., Ltd.) TMPT: Trimethylolpropane triacrylate DPHA: Dipentaerythritol hexaacrylate IPA-ST: IPA-dispersed silica (30 wt%) (Nissan Chemical Co., Ltd.) MEK-ST-40: MEK dispersed silica (40 wt%) (Nissan Chemical Co., Ltd.) Irg184: Irgacure 184 (BASF Japan Ltd.)

[0078] ( 1 H-NMR analysis) Equipment: JEOL Ltd. JNM-ECZ400S Frequency: 400MHz Deuterated solvent: deuterated methanol Reference peak: tetramethylsilane was set at 0.00 ppm.

[0079] (GPC) The weight average molecular weight (Mw) was determined by measuring a chromatogram by gel permeation chromatography (GPC) under the following conditions, and calculating the value converted into the molecular weight of standard polystyrene. GPC equipment: Shimadzu Corporation HPLC Prominence Detector: Differential refractive index detector Column: TSKgel ALPHA-3000 manufactured by Tosoh Corporation Eluent: tetrahydrofuran Eluent flow rate: 0.6 ml / min Column temperature: 40℃ Calibration curve: Created using data from 8 standard polystyrene samples

[0080] (FT-IR) Apparatus: Thermo Fisher Scientific Nicolet iS50 Measurement method: ATR method

[0081] (Adsorption to glass) A 1 wt % ethyl acetate solution of the reactive fluorine-containing oligomer synthesized in Synthesis Examples 1 to 5 below was prepared. A glass was immersed in the solution and then pulled out to form an additive film on the glass. Each glass sample was then immersed in ethyl acetate solvent, removed, and dried. The water contact angle of the dried glass sample was then measured. A contact angle of 40° or less can be considered to indicate that the compound is only slightly adsorbed to the glass.

[0082] (Liquid appearance) The appearance of each coating liquid was visually observed. Evaluation criteria ◯: No silica aggregation is observed and the silica is uniformly dispersed. ×: Silica aggregation is observed.

[0083] (Coating appearance) The coating of each film sample was visually inspected. Evaluation criteria ◯: The coating film is transparent and not cloudy. ×: The coating film is cloudy.

[0084] (Water contact angle measurement) The contact angle of the prepared film sample was measured using DMo-702 (manufactured by Kyowa Interface Science Co., Ltd.) The contact angle is preferably 100° or more.

[0085] <Synthesis Example 1> In a three-necked flask (500 ml) equipped with a condenser, 50 parts by mass of AC-600, 20 parts by mass of PE-90, 30 parts by mass of MMA, 200 parts by mass of butyl acetate, 0.22 parts by mass of lauryl mercaptan, and 0.25 parts by mass of V-601 (oil-soluble azo polymerization initiator, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) were placed. Nitrogen gas was introduced into the reaction solution, and the atmosphere inside the reaction vessel was replaced with nitrogen. After the nitrogen replacement, the reaction solution was heated to 80°C while stirring, and the reaction was initiated. Stirring was then continued at 80°C for 8 hours. The completion of the reaction was confirmed by 1The disappearance of peaks specific to each acrylate in H-NMR was confirmed. 100 mol % of potassium carbonate and 100 mol % of acrylic acid chloride were added to the synthesized fluorine-containing oligomer PE-90, and the reaction solution was stirred at 50°C for 8 hours. 1 The reaction mixture was filtered to remove inorganic compounds, yielding reactive fluorine-containing oligomer 1. The weight-average molecular weight (Mw) of reactive fluorine-containing oligomer 1 measured by GPC was 30,000 in terms of polystyrene. The adsorption of reactive fluorine-containing oligomer 1 to glass was also tested (Table 2).

[0086] <Synthesis Example 2> Reactive fluorine-containing oligomer 2 was synthesized using the same procedure as in Synthesis Example 1, but using the monomer weights shown in Table 1. The weight average molecular weight (Mw) measured by GPC in terms of polystyrene was 30,000. In addition, a test of the adsorption of reactive fluorine-containing oligomer 2 to glass was carried out (Table 2).

[0087] <Synthesis Example 3> In a three-necked flask (500 ml) equipped with a condenser, 50 parts by mass of AC-600, 20 parts by mass of PE-90, 30 parts by mass of MMA, 200 parts by mass of butyl acetate, 0.22 parts by mass of lauryl mercaptan, and 0.25 parts by mass of V-601 (oil-soluble azo polymerization initiator, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) were placed. Nitrogen gas was introduced into the reaction solution, and the atmosphere inside the reaction vessel was replaced with nitrogen. After the nitrogen replacement, the reaction solution was heated to 80°C while stirring, and the reaction was initiated. Stirring was then continued at 80°C for 8 hours. The completion of the reaction was confirmed by 1 The reaction was confirmed by the disappearance of the peaks characteristic of each acrylate in H-NMR. 50 mol% of AOI and 1 mol% of triethylamine were added to the synthesized fluorine-containing oligomer PE-90, and the reaction solution was stirred at 50°C for 8 hours. The completion of the reaction was confirmed by the disappearance of the -N=C=O absorption using FT-IR. The desired reactive fluorine-containing oligomer 3 was obtained. The weight-average molecular weight (Mw) measured by GPC in terms of polystyrene was 30,000. Furthermore, a test of the adsorption of reactive fluorine-containing oligomer 3 to glass was conducted (Table 2).

[0088] <Synthesis Examples 4 and 5> The same procedure as in Synthesis Example 1 was repeated, except that the monomer weights shown in Table 1 were used, to synthesize reactive fluorine-containing oligomers 4 and 5. The weight-average molecular weight (Mw) in terms of polystyrene, measured by GPC, was 30,000. An adsorption test of the reactive fluorine-containing oligomers 4 and 5 on glass was also carried out (Table 2).

[0089] [Table 1]

[0090] [Table 2]

[0091] <Preparation of UV-curable liquid> A UV-curable liquid was prepared with the formulation shown in Table 3.

[0092] [Table 3]

[0093] <Example 1> To the UV-curable liquid, the reactive fluorine-containing oligomer 1 synthesized in Synthesis Example 1 was added so that the active ingredient concentration became 0.3 wt%, and a coating liquid was prepared. The coating liquid was applied to a PET film using a bar coater No. 8. The coated film was dried at 100 °C for 1 minute. The dried film was UV-cured to prepare a film sample. Thereafter, the appearance evaluation of the coating liquid outside the liquid, the appearance evaluation of the coating film of the film sample, and the water contact angle were measured. The results are shown in Table 4.

[0094] <Examples 2 to 4, Comparative Examples 1 to 8> A coating liquid was prepared and a film sample was prepared in the same manner as in Example 1, except that the composition shown in Table ② was changed. Thereafter, the appearance evaluation of the coating liquid outside the liquid, the appearance evaluation of the coating film of the film sample, and the water contact angle were measured. The results are shown in Tables 4 and 5.

[0095] [Table 4]

[0096] [Table 5]

[0097] The fluorine-containing oligomers of Examples 1 to 4 did not have a hydroxyl group or a urethane structure, and therefore had low adsorption to silica, and were able to suppress the aggregation of silica particles. Furthermore, the fluorine-containing oligomers used in Examples 1 to 4 also had low adsorption to glass.

[0098] On the other hand, in Comparative Examples 1 to 8, the silica particles aggregated because compounds having a hydroxyl group and / or a urethane structure were used, and the compounds also had high adsorption to glass.

Claims

1. a hydroxyl group-containing fluorine-based polymer (A); A liquid repellent additive comprising an ester-based reaction product with at least one (meth)acrylate monomer (B) selected from the group consisting of a carboxylic acid halide having a (meth)acrylate group, a carboxylic acid anhydride having a (meth)acrylate group, and a carboxylic acid having a (meth)acrylate group, the reaction ratio of the hydroxyl groups in the hydroxyl group-containing fluorine-based polymer (A) to the (meth)acrylate-based monomer (B) is 1:1.0 to 1:1.5 in terms of molar ratio; 95% or more of the hydroxyl groups in the hydroxyl group-containing fluorine-based polymer (A) are esterified, The hydroxyl group-containing fluorine-based polymer (A) comprises the following (a) to (c): (a) at least one (meth)acrylate monomer containing a perfluoroether moiety; (b) at least one hydroxyl group-containing (meth)acrylate monomer; (c) at least one (meth)acrylate monomer (excluding monomers corresponding to (a) and (b)); It is obtained by copolymerizing the monomers a copolymerization ratio of the monomer (a) and the monomer (b) being 40 to 70 mass% of the monomer (a) and 10 to 40 mass% of the monomer (b), relative to 100 mass% in total of the monomer (a), the monomer (b), and the monomer (c).

2. 2. The liquid repellent additive according to claim 1, wherein the monomer (a) comprises a (meth)acrylate monomer containing one perfluoroether moiety and a (meth)acrylate monomer containing multiple perfluoroether moieties.

3. The liquid repellent additive according to claim 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): 【Chemistry 1】 (In the formula, R 1 represents a hydrogen atom 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 optionally have an ether bond (—O—), an ester bond (—COO— or —O—CO—), or an amide bond (—CONH— or —NHCO—)). R 3 represents a hydrogen atom or a methyl group. R 4 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 optionally have an ether bond (—O—), an ester bond (—COO— or —O—CO—), or an amide bond (—CONH— or —NHCO—)). n is an integer from 1 to 10.

4. The liquid repellent additive according to claim 1, wherein the fluorine content of the hydroxyl group-containing fluorine-based polymer (A) is 20 to 35% by mass.

5. The liquid repellent additive according to claim 1, wherein the (meth)acrylate monomer (B) is a carboxylic acid halide having a (meth)acrylate group.

6. The liquid-repellent additive according to claim 1 , which is dissolved in a solvent.

7. The liquid repellent additive according to claim 1, which is added to a UV curable resin.

8. A liquid-repellent composition comprising a UV-curable resin and the liquid-repellent additive according to claim 1.

9. A liquid-repellent cured resin obtained by irradiating the liquid-repellent composition according to claim 8 with ultraviolet light.

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

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