TWI888535B - Repellents, repellent compositions, hardened resins and articles - Google Patents

Abstract

The subject of the present invention is to provide a repellent that can stably reduce the surface free energy. The means for solving the subject is a repellent, which is composed of a urethane reaction product formed by reacting a fluoropolymer containing a hydroxyl group with at least one (meth)acrylate monomer containing an isocyanate group, and the aforementioned fluoropolymer containing a hydroxyl group is obtained by copolymerizing the following (A) to (C) monomers: (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

Repellents, repellent compositions, hardened resins and articles

The present invention relates to a repellent, a repellent composition, a hardened resin and an article.

In order to use printing technology represented by inkjet to manufacture devices such as pixels or wiring for displays, color filters, biochips, etc., it is necessary to pattern the substrate into repellent areas and lyophilic areas at the micron level by photolithography in advance. In order to obtain the repellent area, a repellent is added to, for example, a UV curable resin composition, a color photoresist, etc.

However, if a high-performance repellent is added to a hardened resin composition, a color photoresist, etc., there are defects such as turbidity of the color photoresist and depressions on the surface of the photoresist.

If the fluorinated oligomer disclosed in Patent Document 1 is added to UV curable resin composition, color photoresist, etc., although the above-mentioned turbidity or collapse will not occur, the liquid repellency will be insufficient. Prior Art Documents Patent Documents

Patent document 1: Japanese Patent No. 5997998

Problem to be solved by the invention The purpose of the invention is to provide a repellent, a repellent composition, a hardened resin and an article that can stably reduce the surface free energy.

Means for Solving the Problem The present invention provides the following repellents, repellent compositions, hardened resins and articles. Item 1. A repellent, which is composed of a urethane reaction product formed by reacting a fluoropolymer containing a hydroxyl group with at least one (meth)acrylate monomer containing an isocyanate group, and the aforementioned fluoropolymer containing a hydroxyl group is obtained by copolymerizing the following (A) to (C) monomers: (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. Item 2. The repellent as in Item 1, wherein (A) comprises: a (meth)acrylate monomer containing one perfluoroether portion and a (meth)acrylate monomer containing a plurality of perfluoroether portions. Item 3. The 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): [Chemical Formula 1] (wherein, ^R1 represents H or methyl; ^R2 represents a divalent saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms (the saturated aliphatic hydrocarbon group is a linear or branched type, and is a saturated aliphatic hydrocarbon group, a saturated aliphatic hydrocarbon group having an ether bond (-O-), a saturated aliphatic hydrocarbon group having an ester bond (-COO- or -O-CO-), or a saturated aliphatic hydrocarbon group having an amide bond (-CONH- or -NHCO-)); ^R3 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 linear or branched type and is a saturated aliphatic hydrocarbon group, a saturated aliphatic hydrocarbon group having an ether bond (-O-), a saturated aliphatic hydrocarbon group having an ester bond (-COO- or -O-CO-), or a saturated aliphatic hydrocarbon group having an amide bond (-CONH- or -NHCO-); n is an integer from 1 to 10). Item 4. The repellent according to any one of Items 1 to 3, wherein the fluorine content of the hydroxyl-containing fluorine-based polymer is 20 to 35% by mass. Item 5. The repellent according to any one of Items 1 to 4, which is dissolved in a solvent. Item 6. A repellent as described in any one of Items 1 to 5, which is added to a UV curable resin. Item 7. A repellent composition comprising a UV curable resin and a repellent as described in any one of Items 1 to 5. Item 8. A repellent curable resin, which is obtained by irradiating the repellent composition as described in Item 7 with ultraviolet rays. Item 9. An article, which comprises the repellent curable resin as described in Item 8.

Effect of the invention By adding the repellent of the present invention to a UV curable resin composition, a color photoresist, etc., and curing the obtained composition, a hardened surface with greatly reduced free energy can be formed, and the free energy of the obtained hardened surface has little change over time.

When the repellent of the present invention is added to a UV curable resin or a color resist, and the composition is applied to a substrate or the like and cured, the curing component contained in the UV curable resin or the color resist reacts with the repellent of the present invention, thereby imparting repellency to the cured resin of the obtained cured film or the like.

・Component (A) Regarding the perfluoroether portion of the (meth)acrylate monomer, there can be mentioned -O-(perfluoroalkyl), -O-(perfluoroalkylene), (perfluoroalkylene)-O-(perfluoroalkylene), etc.

Specific examples of the perfluoroalkyl group include _-CF3 , _-CF2CF3 , _-CF2CF2CF3 , -CF( _{CF3 )2 , -CF2CF2CF2CF3 and the like} , linear or branched _{C1 - C8 perfluoroalkyl} groups, among which _C1 - _C4 perfluoroalkyl groups are preferred.

Specific examples of the perfluoroalkylene group include linear or branched divalent _C2 - _C8 perfluoroalkylene groups such as _-CF2- , _{-CF2CF2- , -CF} ( _CF3 )-, _{-CF2CF2CF2- , -CF2CF} ( _CF3 )-, _{-CF ( CF3} ) _CF2- , _{-CF2CF2CF2CF3-} , among which _{C2 - C4} perfluoroalkylene groups are preferred.

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

[Chemical formula 2] (In the formula, ^R1 represents H or a methyl group; ^R2 represents a divalent saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms (the saturated aliphatic hydrocarbon group may be a linear or branched type, and may have an ether bond (-O-), an ester bond (-COO- or -O-CO-), or an amide bond (-CONH- or -NHCO-) as desired); ^R3 represents H or a methyl group; ^R4 represents a divalent saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms (the saturated aliphatic hydrocarbon group may be a linear or branched type, and may have an ether bond (-O-), an ester bond (-COO- or -O-CO-), or an amide bond (-CONH- or -NHCO-) as desired); n is an integer from 1 to 10). Among them, n is preferably 2-10, more preferably 3-9, more preferably 4-8, and particularly preferably 5-7.

Examples of the divalent saturated aliphatic hydrocarbon group include _-CH2- , _{-CH2CH2- , -CH} ( _CH3 )-, _{-CH2CH2CH2- , -CH2CH} (CH3)-, -CH( _CH3 ) _CH2- , _{-CH2CH2CH2CH3-} and _{the like ,} divalent saturated aliphatic hydrocarbon groups having _C1 to _C10 , preferably _C1 to _C6 , _and more preferably _C1 to _C4 .

_Furthermore , examples of the divalent saturated aliphatic hydrocarbon group having an ether bond include _-CH2 -O _{- CH2CH2-} , -CH2CH2- _{O- CH2-} , and -( _CH2CH2 - _O ) _1- (l is an integer of 1 to 5). Examples of the divalent saturated aliphatic hydrocarbon group having an ester bond include _{-CH2CH2- COO- ,} -CH2CH2- _OCO- , _{-CH2CH2CH2 - COO-} , -CH2CH2CH2 _{- OCO-} , -CH2CH2 _- COO _{- CH2- ,} and -CH2CH2 _{- OCO} - _CH2- . Examples of the divalent saturated aliphatic hydrocarbon group having an amide bond include -CH ₂ CH ₂ -NHCO-, -CH ₂ CH ₂ -CONH-, -CH ₂ -NHCO-CH ₂ -, and -CH ₂ -CONH-CH ₂ -.

Regarding the (meth)acrylate monomer containing a perfluoroether moiety, one kind may be used alone or two or more kinds may be used in combination.

・Component (B) The number of hydroxyl groups in the hydroxyl-containing (meth)acrylate monomer is 1 or 2, preferably 1. Examples of the hydroxyl-containing (meth)acrylate monomer include compounds represented by the following formula (B1):

[Chemical formula 3] (In the formula, R ⁵ represents H or a methyl group; R ⁶ represents a linear or branched alkylene group; m represents an integer of 1 to 20). These may be used alone or in combination of two or more.

Examples of the linear or branched alkylene group include C 1 to C 4 alkylene groups such as -CH ₂ -, -CH ₂ CH ₂ -, -CH(CH ₃ )-, -CH ₂ CH ₂ CH ₂ -, -CH ₂ CH(CH ₃ )-, -CH(CH ₃ )CH ₂ -, and -CH ₂ CH ₂ CH ₂ CH _{3 - .}

・Component (C) As for the (meth)acrylate monomer, there can be mentioned methyl acrylate (MA), ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate (4-HBMA), isobutyl acrylate, dibutyl acrylate, tertiary 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, benzyl methacrylate, and these may be used alone or in combination of two or more.

・Fluorine-based polymer containing a hydroxyl group The fluorine-based polymer containing a hydroxyl group can be obtained by copolymerizing the above-mentioned component (A), component (B), and component (C). The copolymerization reaction is smoothly carried out by reacting at 70 to 90°C for 4 to 12 hours in the presence of a free radical initiator. Regarding the free radical initiator, it is preferable to carry out the polymerization in the presence of a free radical polymerization initiator. As for the free radical polymerization initiator which can be used in the production method of the present invention, for example, tertiary butyl peroxide, isopropylbenzene hydroperoxide, 2,5-dihydroperoxy-2,5-dimethylhexane, diisopropylbenzene peroxide, di(tertiary butyl) peroxide, tertiary butyl peroxybutyrate, tertiary butyl peroxide-α-isopropylbenzene, di-α-isopropylbenzene peroxide, α,α'-bis(tertiary butyl peroxide)-p-diisopropylbenzene, 2,5-dimethyl-2,5-di(tertiary butyl peroxide)hexane, 2,5-dimethyl-2,5-di(tertiary butyl peroxide)-hexyne-3-peroxyacetyl, succinic acid peroxide, diisobutylene peroxide, lauryl peroxide, benzoyl peroxide, tertiary butyl peroxyacetate, peroxy Tertiary butyl isobutyrate, diisobutyl peroxydicarbonate, tertiary butyl peroxyisopropyl carbonate, methyl ethyl ketone peroxide, cyclohexanone peroxide, 2,2'-azobisisobutyronitrile, dimethyl = 2,2'-azobisisobutyrate, dimethyl azobisisobutyrate (V-601), 2,2'-azobis (2-methylbutyronitrile), 2,2'-azobis ( Azo compounds such as isobutylamidine) dihydrochloride, 2,2'-azobis[2-(2-imidazolin-2-yl)propane] and its disulfate, 2,2'-azobis(2-methylamidoximine) dihydrochloride, potassium persulfate, sodium persulfate, ammonium persulfate, potassium persulfate, tertiary butyl peroxide, benzoyl peroxide, isopropylbenzene hydroperoxide, etc. These free radical polymerization initiators can be used alone or in combination of two or more. Chain transfer agents such as lauryl mercaptan, octyl mercaptan, dodecyl mercaptan, 2-hydrothioethanol, octyl hydrothioacetate, 3-hydrothiopropionic acid, and thioglycerol can also be used in the copolymerization reaction to adjust the molecular weight.

Regarding the ratio of component (A), component (B), and component (C) used to prepare the hydroxyl-containing fluorine-based polymer, with the total of these being 100 mass%, Component (A): preferably 40 to 70 mass%, preferably 50 to 60 mass%, Component (B): preferably 10 to 40 mass%, preferably 20 to 30 mass%, Component (C): preferably 10 to 40 mass%, preferably 20 to 30 mass%.

In the component (A) used to prepare the hydroxyl-containing fluorine-based polymer, the mass ratio of the monomer represented by the formula (A1) to the monomer represented by the formula (A2) is preferably monomer (A1):monomer (A2)=1:0 to 1:0.4. If the amount of the component (A2) relative to the component (A1) is too large, the liquid will become turbid and the appearance of the liquid will deteriorate.

The fluorine content of the hydroxyl-containing fluorine-based polymer is preferably 15-40 mass %, more preferably 20-35 mass %, and even more preferably 22-32 mass %. If the fluorine content is too high, the surface of the hardened resin obtained after mixing with the UV hardening resin and hardening will collapse and be poor. If the fluorine content is too low, the liquid repellency will be reduced and be poor.

The weight average molecular weight of the hydroxyl-containing fluorine-based polymer is preferably 3000-50000, more preferably 10000-20000. The weight average molecular weight can be calculated by converting the molecular weight of the standard polystyrene by gel permeation chromatography (GPC).

・(Meth)acrylate monomers containing isocyanate groups Examples of (meth)acrylate monomers containing isocyanate groups include 2-isocyanatoethyl (meth)acrylate, 2-isocyanatopropyl (meth)acrylate, 3-isocyanatopropyl (meth)acrylate, 1-methyl-2-isocyanatoethyl (meth)acrylate, 1,1-dimethyl-2-isocyanatoethyl (meth)acrylate, 4-isocyanatocyclohexyl (meth)acrylate, 2-(2-(meth)acryloyloxy)-1-(methyl)-2-isocyanatoethyl (meth)acrylate, Ethoxy)ethyl isocyanate, 1,1-(bis(meth)acryloyloxymethyl)ethyl isocyanate, 2-(2-(meth)acryloyloxyethoxy)ethyl isocyanate, 1,1-(bis(meth)acryloyloxymethyl)ethyl isocyanate, 2-(2-isocyanatoethoxy)ethyl (meth)acrylate, 2-(2-isocyanatoethoxy) (meth)acrylate, etc. Among them, 2-isocyanatoethyl (meth)acrylate is preferred. The (meth)acrylate monomer containing an isocyanate group can be used alone or in combination of two or more.

・Urethane reaction products Urethane reaction products can be prepared by reacting a fluoropolymer containing a hydroxyl group with a (meth)acrylate monomer containing an isocyanate group in the presence of an amine catalyst as needed. Examples of the amine catalyst include triethylamine, N-methylmorpholine, N-ethylmorpholine, N,N'-dimethylpiperidinium, dimethylbenzylamine, N,N'-dimethylethanolamine, and bis(dimethylaminoethyl)ether. For each equivalent of hydroxyl group in the fluoropolymer containing a hydroxyl group, 0.3 to 1.0 equivalent of the (meth)acrylate monomer containing an isocyanate group is used and the reaction is carried out at 50 to 80°C for 4 to 8 hours to facilitate the reaction.

・Repellent, repellent composition, hardened resin, article The repellent of the present invention is preferably a liquid repellent containing a urethane reaction product and further containing a solvent. As for the solvent, there may be mentioned dichloromethane, 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, 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 thiocyanate, thiocyanate acetate, butyl thiocyanate, butyl carbitol, carbitol acetate, ethyl lactate, isopropyl alcohol, methanol, ethanol, pentane, hexane, heptane, octane, cyclohexane, benzene, toluene, xylene, anisole, tetrahydronaphthalene, cyclohexylbenzene, symmetrical trimethylbenzene, petroleum ether, tetrahydrofuran, 1,4-dioxane, etc.

The repellent of the present invention can be added to a UV curable resin to prepare a repellent composition. The UV curable resin and the repellent composition are preferably in liquid form. The repellent composition can be hardened to impart repellency to the hardened resin. The urethane reaction product of the present invention can be added to a UV curable resin to impart repellency to the hardened product, and is therefore very useful as a repellent additive for UV curable resins.

The repellent of the present invention has a continuous repellent property. For example, when the repellent is mixed with a hardening resin to prepare a repellent composition and the repellent composition is hardened to prepare a hardening resin (hardening film), the absolute value of the change rate between the initial surface free energy (SFE ₀ ) of the hardening resin and the surface free energy (SFE ₃ ) after 3 days (shown in Formula X) is less than 10%, preferably less than 5%, more preferably less than 4%, and particularly preferably less than 3%.

[Mathematical formula 1]

Regarding UV curing resin, acrylic resin, epoxy resin, melamine resin, etc. can be used. A better implementation form of UV curing resin is used for the manufacture of color filters, color photoresists, etc. Color photoresists include photoresists (black photoresists) used to manufacture black matrices. In order to meet the physical properties of heat resistance, hot water resistance, and chemical resistance, UV curing resins can also be curing resins with two or more functions. In order to obtain a low-viscosity, liquid repellent composition, UV curing resins with low molecular weight and exhibiting amorphous properties are preferred.

The repellent composition of the present invention preferably contains 20-40% of the UV curable resin (solid content) and 0.05-2.0% of the solid content of the repellent agent, based on the total solid content as 100% by mass. It is more preferably 25-35% of the UV curable resin (solid content) and 0.2-0.7% of the solid content of the repellent agent.

The repellent composition of the present invention can be cured by irradiating UV (ultraviolet rays) to produce a repellent curing resin. The curing can be carried out under the curing conditions of the UV curing resin. In a preferred embodiment, the liquid repellent composition of the present invention is applied to a substrate and cured by UV to produce an article having a cured film in the form of a cured resin. This cured film has a repellent surface. As for the substrate, silicon wafers, synthetic resins, glass, metals, ceramics, etc. can be cited. The synthetic resin can be any of a thermoplastic resin and a thermosetting resin. Examples of glass include silicate glass, alkali silicate glass, sodium calcium glass, potassium calcium glass, lead glass, barium glass, borosilicate glass, etc. Examples of metal include gold, silver, copper, iron, nickel, aluminum, platinum, etc. Examples of ceramics include oxides (e.g., aluminum oxide, zinc oxide, titanium oxide, silicon oxide, zirconium oxide, barium titanate), nitrides (e.g., silicon nitride, boron nitride), sulfides (e.g., cadmium sulfide), and carbides (e.g., silicon carbide).

The method of applying the repellent composition to the substrate may be, for example, roller coating, gravure coating, micro-gravure coating, flow coating, rod coating, spray coating, die coating, spin coating, dip coating, etc. The method may be selected in consideration of the type, shape, productivity, adjustability of film thickness, etc. of the substrate.

Embodiments The present invention is described in detail with the following embodiments.

Materials used 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 [Chemical formula 4]

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]-) [Formula 5]

PE-90: Poly(oxy-1,2-ethanediyl), α-(2-methyl-1-oxo-2-propen-1-yl)-ω-hydroxy- [Chemical formula 6]

4-HBMA: 2-Propenoic acid, 2-methyl-, 4-hydroxybutyl ester [Formula 7]

MMA: 2-Propenoic acid, 2-methyl-, methyl ester [Formula 8]

PME-200: Poly(oxy-1,2-ethanediyl), α-(2-methyl-1-oxo-2-propen-1-yl)-ω-methoxy- [Chemical formula 9]

Karenz AOI: 2-Isocyanatoethyl acrylate [Chemical formula 10]

Ftergent 601ADH2: (manufactured by NEOS Co., Ltd.)

Synthesis Example 1 Add AC-500 (50g), PE-90 (20g), MMA (20g), butyl acetate (200g), lauryl mercaptan (1.48g), and V-601 (0.84g) into a three-necked flask (500ml) equipped with a cooling tube. Introduce nitrogen into the reaction solution and replace the nitrogen in the reaction container. After nitrogen replacement, heat the reaction solution to 80°C while stirring the reaction solution to start the reaction. Then continue stirring at 80°C for 8 hours. The end of the reaction is confirmed by the disappearance of the characteristic peaks of each acrylate in ^1H -NMR. A quantitative target fluorinated oligomer is obtained. 50 mol% of Karenz AOI and 1 mol% of triethylamine were added to PE-90, and the reaction solution was stirred at 50°C for 8 hours. The end of the reaction was confirmed by the disappearance of -N=C=O absorption using FT-IR. A quantitative amount of the target urethane-based reaction product, the reactive fluorinated oligomer 1, was obtained.

Synthesis Examples 2 to 9 The same operation as in Synthesis Example 1 was followed, except that the monomer weights were changed to those listed in Table 1 to synthesize reactive fluorinated oligomers 2 to 9.

Synthesis Example 10 Ftergent 601ADH2 is used as the reactive fluorinated oligomer 10.

Table 1

Examples 1 to 5 and Comparative Examples 1 to 5 For the active ingredient of the photoresist coating liquid, the reactive fluorinated oligomers 1 to 9 synthesized in Synthesis Examples 1 to 9 were added to make the active ingredient of the repellent agent have a concentration of 0.5 wt%. The coating liquid was spin-coated, applied to a glass substrate, and then heated and dried, and then irradiated with UV to prepare a coating film, and the following evaluation was performed. The results are shown in Table 2.

Examples 6-10 and Comparative Examples 6-9 For the active ingredient of the UV curable hard coating liquid containing dipentatyritol hexaacrylate, the reactive fluorinated oligomers 1-9 synthesized in Synthesis Examples 1-9 were added to make the active ingredient of the repellent agent have a concentration of 0.5wt%. The hard coating liquid was applied to a PET substrate by bar coating, and then heated and dried, and then UV irradiated to prepare a coating film, and the following evaluation was performed. The results are shown in Table 3.

Evaluation Film appearance The film appearance of each coating film was visually observed, and a score of 0 was given when there was no film collapse, and a score of × was given when there was collapse or more.

Surface free energy measurement The contact angle of the produced coating is measured to calculate the surface free energy. The calculation formula uses the Kaelble-Uy formula. As long as the initial surface free energy is 17mN/m or less, the performance is good.

Film performance stability The prepared 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.

Compare the initial and post-storage surface free energies. If the change in surface free E after 3 days is less than 1mN/m, it is 0. If the change in surface free E after 3 days is more than 1mN/m, it is ×.

Table 2

Table 3

As shown in Table 2, the Ftergent 601ADH2 used in 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 good. The repellent of the present invention has a very low initial SFE, and the SFE change rate after 3 days relative to the initial SFE is less than 5%, which is obviously quite good for imparting repellency to photoresist coating materials.

As shown in Table 3, for UV curable hard coating, Examples 6 to 10 have good film appearance and good initial SFE. Comparative Examples 6 to 9 have film collapse. It is obvious that the repellent of the present invention is a good repellent for imparting repellency to UV curable hard coating.

Claims (8)

A repellent is composed of a urethane reaction product formed by reacting a fluoropolymer containing a hydroxyl group with at least one (meth)acrylate monomer containing an isocyanate group, wherein the fluoropolymer containing a hydroxyl group is copolymerized from the following monomers (A) to (C); (A) the (meth)acrylate monomer containing a perfluoroether portion comprises 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): (wherein, ^R1 represents H or methyl; ^R2 represents a divalent saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms (the saturated aliphatic hydrocarbon group is a linear or branched type, and is a saturated aliphatic hydrocarbon group, a saturated aliphatic hydrocarbon group having an ether bond (-O-), a saturated aliphatic hydrocarbon group having an ester bond (-COO- or -O-CO-), or a saturated aliphatic hydrocarbon group having an amide bond (-CONH- or -NHCO-)); ^R3 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 linear or branched type and is a saturated aliphatic hydrocarbon group, a saturated aliphatic hydrocarbon group having an ether bond (-O-), a saturated aliphatic hydrocarbon group having an ester bond (-COO- or -O-CO-), or a saturated aliphatic hydrocarbon group having an amide bond (-CONH- or -NHCO-)); n is an integer from 1 to 10); (B) at least one hydroxyl-containing (meth)acrylate monomer, comprising a monomer represented by the following formula (B1): (wherein, R ⁵ represents H or methyl; R ⁶ represents a linear or branched alkylene group; m represents an integer of 1 to 20); (C) 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, dibutyl acrylate, tertiary 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; Furthermore, taking the total amount of the aforementioned monomer (A), the aforementioned monomer (B) and the aforementioned monomer (C) as 100 mass %, the aforementioned monomer (A) is 40-60 mass % and the mass ratio of the monomer (A1) to the monomer (A2) is 1:0 to 1:0.4, the aforementioned monomer (B) is 10-40 mass %, and the aforementioned monomer (C) is 10-40 mass %. The repellent of claim 1, wherein the urethane reaction product is obtained by reacting 0.3-1.0 equivalents of a (meth) acrylic monomer containing an isocyanate group with 1 equivalent of a hydroxyl group of a fluoropolymer containing a hydroxyl group. The repellent of claim 1, wherein the fluorine content of the hydroxyl-containing fluorine-based polymer is 20-35 mass %. For example, the diuretic in claim 1 is prepared by dissolving it in a solvent. The repellent of claim 1 is added to a UV curing resin for use. A repellent composition comprises a UV curable resin and the repellent agent of claim 1. A repellent hardening resin is obtained by irradiating the repellent composition of claim 6 with ultraviolet rays. An article containing a repellent hardening resin, comprising the repellent hardening resin as claimed in claim 7.