WO2011129426A1 - Agent for imparting antifouling properties - Google Patents

Abstract

Disclosed is an agent for imparting antifouling properties, which is obtained by the copolymerization of a monomer (A), a monomer (B), and a monomer (C), wherein monomer (A) is a fluorine-containing (meth) acrylate, monomer (B) is a silicone-containing (meth) acrylate, and monomer (C) is a (meth) acrylate other than the aforementioned (meth) acrylates.

Description

Antifouling agent

The present invention relates to a novel fluorine-containing silicone copolymer useful as a surface treatment agent and a surface modifier for imparting antifouling properties to be used in the fields of glass, fibers, metals, resins, films, optical materials, paints and the like. About.

Coating liquids used in the fields of resins, optical materials, paints, etc., suppress defects such as streaks, repellency, unevenness, irregularities, and non-wetting that occur during the coating process on the surface of the member. Various substances are added for the purpose of imparting smoothness to the film surface.

A compound containing a perfluoroalkenyl group is also used as an additive in this application, and in particular, a nonionic surfactant having a perfluoroalkenyl group is known to be useful in terms of imparting surface smoothness. (For example, Patent Document 1).

Thin displays, PC monitors, mobile phones, portable game consoles, car navigation systems, etc. are used in various environments, especially on the screens of devices that have become touch panels, such as fingerprints, magic inks, cosmetics, etc. Easy to get dirty.

問題 Problems caused by the adhesion of fingerprints, magic ink, cosmetics, etc. include a decrease in screen transparency and a decrease in image clarity. Wipe off with a cloth soaked in water or detergent to remove stains such as fingerprints, magic ink, and cosmetics, but it is not easy to wipe off the stains. Scratches may occur.

As one means for preventing or removing dirt, a method for improving the water and oil repellency of the screen surface has been proposed. As a useful method thereof, a method of introducing a fluorine compound or a silicon compound is proposed. The method of introducing is known and widely used (for example, Patent Document 2).

However, although fluorine compounds can provide surface smoothness and fingerprint wiping properties, there are problems with poor magic ink wiping properties, and silicon compounds provide improved surface slipping, magic ink wiping properties, and scratch resistance. However, there was a problem that the fingerprint wiping property was poor.

In addition, the fluorine compound and the silicon compound have extremely poor compatibility and are liable to cause phase separation. There are problems such as a region in which the fluorine compound is aggregated on the surface by the phase separation and a region in which the fluorine compound is aggregated (white turbidity), resulting in a decrease in surface visibility. Therefore, a sufficient amount of fluorine compound for imparting antifouling properties could not be mixed with the silicon compound.

On the other hand, many techniques for introducing a compound partially having a fluorine group added into a silicone compound have been proposed (for example, Patent Document 3). Since this technique is a technique of introducing fluorine or the like into various types of silicon compounds, there is an advantage that the degree of freedom in design is high, but since it is a special compound, it cannot be easily obtained. In addition, since such a compound does not chemically bond with the curing component in the coating liquid, it will escape from the cured resin film over time or with an external stimulus, and the water / oil repellent effect will be lost. Furthermore, there is a problem that it exhibits a plasticizer action in the film and lowers the film strength.

Furthermore, no fluorine-containing or silicone-containing copolymer having a perfluoroalkyl group or a perfluoroalkenyl group highly branched in the main chain has been reported.

JP 2008-77057 A Japanese Patent No. 4401509 JP 2009-29882 A

An object of the present invention is to provide an antifouling property-imparting agent that has solved the above-mentioned problems of the prior art.

As a result of intensive studies to solve these problems, the present inventor has found that a copolymer containing a fluorine-containing (meth) acrylate, a silicon-containing (meth) acrylate and an alkylene oxide (meth) acrylate, and a curable resin component Provided a copolymer that can continuously impart water and oil repellency to the coating surface by introducing reactive functional groups (hydroxyl, terminal carbon-carbon double bond, etc.) that can be chemically bonded to By doing so, it was found that it can be easily dissolved in the coating material, and that surface smoothness, antifouling property and water / oil repellency can be continuously imparted when the coating material is applied. These findings led to the development of copolymers and resin compositions that have both antifouling and leveling effects with excellent sustainability when cured and do not affect film strength. That is, the present invention relates to an antifouling agent and the antifouling resin composition comprising the antifouling agent of the following items 1 to 11 as an active ingredient.
Item 1. An antifouling agent containing a (meth) acrylate copolymer containing the following monomer (A), monomer (B), and optional monomer (C) as a copolymerization component.

Monomer (A): Fluorine-containing (meth) acrylate

[Wherein Rf represents a perfluoroalkyl group or a perfluoroalkenyl group having 1 to 9 carbon atoms, R ¹ represents H or CH ₃ , and R ² represents a divalent saturated fat having 1 to 50 carbon atoms. Aromatic hydrocarbon group (the divalent saturated aliphatic hydrocarbon group may be substituted with a halogen atom or an aryl group, and the divalent saturated aliphatic hydrocarbon group is an ether bond (—O—) , A thioether bond (—S—), an ester bond (—COO— or —O—CO—), an amide bond (—CONH— or —NHCO—) and an arylene group. And Y is a single bond, an ester bond (—COO— or —O—CO—), an amide bond (—CONH— or —NHCO—), a sulfonate ester bond (— S ₂ -O- or _-O-SO 2 -), sulfonamide bond _(-SO 2 NH- or -NHSO ₂ -), indicating an ether bond (-O-) or a thioether bond (-S-). ]
Monomer (B): Silicone-containing (meth) acrylate Monomer (C): (meth) acrylate other than those above 2. Item 2. The antifouling property-imparting agent according to Item 1, wherein the copolymer is further added with a compound (D) having a reactive functional group.
Item 3. When the monomer composition of the copolymer is 100% by mass of the entire copolymer, the monomer (A) is 1 to 50% by mass, the monomer (B) is 1 to 50% by mass, Item 2. The antifouling agent according to Item 1, wherein the monomer (C) is 1 to 90% by mass and the monomer ratio is (B) / (A)> 0.3.
Item 4. When the monomer composition of the copolymer is 100% by mass of the entire copolymer, the monomer (A) is 1 to 50% by mass, the monomer (B) is 1 to 50% by mass, The body (C) is 1 to 90% by mass, the compound (D) having a reactive functional group is 0 to 50% by mass, and the monomer ratio is (B) / (A)> 0.3. Item 3. The antifouling agent according to Item 1 or 2.
Item 5. Item 5. The monomer according to any one of Items 1 to 4, wherein Rf of the monomer (A) is a mixture of (meth) acrylate (A1) having a perfluoroalkyl group and (meth) acrylate (A2) having a perfluoroalkenyl group. Antifouling agent.
Item 6. Item 5. The antifouling agent according to any one of Items 1 to 4, wherein Rf of the monomer (A) is a perfluoroalkenyl group having up to 9 carbon atoms represented by the following formula.

Item 7. Item 7. The antifouling agent according to any one of Items 1 to 6, wherein the monomer (B) is a silicone-containing (meth) acrylate represented by the following formula.

[Wherein, R ¹ represents H or CH ₃ , R ² represents a divalent alkylene group having 1 to 10 carbon atoms, an alkylene oxide group, or a divalent arylene group which may have a substituent, Y represents a single bond, an ester bond (—COO— or —O—CO—), an amide bond (—CONH— or —NHCO—), a sulfonate ester bond (—SO ₂ —O— or —O—SO ₂ —). ), Sulfonamide bond (—SO ₂ NH— or —NHSO ₂ —), ether bond (—O—) or thioether bond (—S—), and R ³ , R ⁴ , and R ⁵ are the same or different. Each is H or an alkyl group having 1 to 8 carbon atoms or

(R ⁷ to R ⁹ are each H or an alkyl group having 1 to 8 carbon atoms, and p is an integer of 1 or more). ]
Item 8. Monomer (C) is an alkylene oxide-containing (meth) acrylate represented by the following formula

[Wherein, R ¹ represents H or CH ₃ , AO represents a divalent alkylene oxide having 2 to 4 carbon atoms, and the group represented by — (AO) n— represents an alkylene having 2 to 4 carbon atoms] 1 or 2 or more types of polymers of oxides (in the case of polymers of 2 or more types of alkylene oxides, each alkylene oxide may be polymerized in block form or randomly), and n Represents an integer of 2 to 20, and W represents an alkoxy group, an aryl group which may have a substituent, a hydroxyl group, a carboxy group (COOH), an amino group or a mercapto group]. Antifouling property-imparting agent according to crab.

Item 9. Item 9. The antifouling agent according to any one of Items 2 to 8, wherein the compound (D) having a reactive functional group is a (meth) acrylate having a functional group (W ¹ ) represented by the following formula.

[Wherein R ¹ represents H or CH ₃ , R ⁶ represents an alkylene group or a divalent arylene group which may have a substituent, and W ¹ represents an isocyanate group, a glycidyl group, an oxetane group, a lactone, Group or phosphate group]
Item 10. Item 10. An antifouling resin composition comprising the antifouling property-imparting agent according to any one of Items 1 to 9 and a resin.
Item 11. Item 11. The antifouling resin composition according to Item 10, wherein the resin is energy curable or thermosetting.

According to the present invention, it is useful as a surface modifier for resins, films, fibers, glass, metals, etc., and has smoothness, water and oil repellency, antifouling properties (fingerprint wiping properties and magic ink wiping properties) on their surfaces. Etc.), a fluorine-containing silicone copolymer (containing fluorine-silicone-alkylene oxide) capable of imparting slipperiness is provided. The fluorine-containing silicone copolymer of the present invention can have a reactive group in the molecule, and the surface modification effect by strengthening the adhesion using a chemical bond to the substrate surface (surface of resin, film, etc.) component High sustainability can be expected. Further, by controlling the amount of reactive groups in the molecule, reaction conditions, monomer type, etc., it is possible to improve the film strength as a surface modifier and to design the strength according to the purpose. Furthermore, the fluorine-containing silicone copolymer of the present invention can also improve the solubility in a solvent during surface modification by introducing a hydrocarbon-based substituent, a hydrophilic substituent or the like into the molecule.

Hereinafter, the antifouling property imparting agent and the resin composition of the present invention will be described in detail.

In this specification, (meth) acrylate means acrylate and / or methacrylate.

Antifouling property imparting agent The antifouling property imparting agent of the present invention is characterized by being a copolymer of the following monomer (A), monomer (B), and monomer (C).

Monomer (A): Fluorine-containing (meth) acrylate Monomer (B): Silicone-containing (meth) acrylate Monomer (C): (meth) acrylate other than the above Fluorine-containing monomer (A) ( The (meth) acrylate is represented by the following formula.

In the formula, Rf represents a perfluoroalkyl group or a perfluoroalkenyl group having 1 to 9 carbon atoms. The perfluoroalkyl group may be either straight-chain, _{branched-chain, CF 3 -, C 2 F} 5 -, (n- or _{iso-) C 3 F 7 -,} (n-, iso-, sec - or _{tert-) C 4 F 9 -,} CF 3 (CF 2) m - (m is 4-8 _{integer), (CF 3) 2 CF} (CF 2) k - (k is an integer of 1-6) Etc.

In the case of a perfluoroalkenyl group, the following three groups are preferably exemplified.

In the formula, R ¹ represents H or CH ₃ .

In the formula, R ² represents a divalent saturated aliphatic hydrocarbon group having 1 to 50 carbon atoms (the divalent saturated aliphatic hydrocarbon group may be substituted with a halogen atom or an aryl group, and The divalent saturated aliphatic hydrocarbon group includes an ether bond (—O—), a thioether bond (—S—), an ester bond (—COO— or —O—CO—), an amide bond (—CONH— or — NHCO—) and at least one divalent group selected from the group consisting of an arylene group), and Y is a single bond, an ester bond (—COO— or —O—CO—) Amide bond (—CONH— or —NHCO—), sulfonic acid ester bond (—SO ₂ —O— or —O—SO ₂ —), sulfonamide bond (—SO ₂ NH— or —NHSO ₂ —), ether Combined ( O-), shows a thioether bond (-S-). The saturated aliphatic hydrocarbon group of the “divalent saturated aliphatic hydrocarbon group having 1 to 50 carbon atoms” may be linear, branched or cyclic. Examples thereof include a methylene group, an ethylene group, a propylene group, a butylene group, a cyclopentylene group, a cyclohexylene group, and an octylene group. Moreover, these saturated aliphatic hydrocarbon groups may have one or a plurality of substituents, and the substituents are not particularly limited as long as they do not adversely affect the present invention. Examples of the substituent include a halogen atom, an aryl group, an alkyl group having 1 to 3 carbon atoms, and an alkoxy group having 1 to 4 carbon atoms. Examples of the arylene group include a phenylene group and a naphthylene group. The arylene group may have a substituent, and the substituent is not particularly limited as long as it does not adversely affect the present invention.

The divalent saturated aliphatic hydrocarbon group includes an ether bond (—O—), a thioether bond (—S—), an ester bond (—COO— or —O—CO—), an amide bond (—CONH— or — It may be interposed with at least one divalent group selected from the group consisting of NHCO-) and arylene groups. “Selected from the group consisting of an ether bond (—O—), a thioether bond (—S—), an ester bond (—COO— or —O—CO—), an amide bond (—CONH— or —NHCO—) and an arylene group. Specific examples of the case of “intervening with at least one divalent group”
(i) -O-, thioether bond (-S-), ester bond (-COO- or -O-CO-), amide bond (-CONH- or -NHCO-), one divalent arylene group When intervening in the group,
(Ii) -O- (arylene)-, -S- (arylene)-, -COO- (arylene)-, -O-CO- (arylene)-, -CONH- (arylene)-, -NHCO- (arylene) )-,-(Arylene) -O-,-(arylene) -S-,-(arylene) -COO-,-(arylene) -O-CO-,-(arylene) -CONH-,-(arylene)- When two divalent groups are interposed side by side, such as NHCO-
(iii) -O- (arylene) -COO-, -COO- (arylene) -O-, -COO- (arylene) -CONH-, -CONH- (arylene) -O-, -NHCO- (arylene)- O-, -O-CO- (arylene) -COO-, -NHCO- (arylene) -O-, -O- (arylene) -O-, -S- (arylene) -S-, -S- (arylene) When intervened by three divalent groups such as) -COO-
Is mentioned.

For example, Synthesis Example 11 fluorinated methacrylate used _in: in _{(A-3 RfOC 6 H 4} CO 2 (CH 2) 2 OC (= O) C (CH 3) = CH 2), Y is O, R2 is - C ₆ H ₄ CO ₂ (CH ₂ ) ₂ —, and R 2 is a divalent saturated aliphatic hydrocarbon group (((C ₆ H ₄ CO ₂ —) interposed between two divalent groups (— is a CH _{2) 2).}

As a preferable specific example of the monomer (A), RfOC ₆ H ₄ CO ₂ (CH ₂ ) ₂ OC (═O) C (CH ₃ ) ═CH ₂ , CF ₃ (CF ₂ ) ₅ CH ₂ CH ₂ OC _{(= O) CH = CH 2} ), RfOC 6 H 4 CO 2 (CH 2) 2 OC (= O) C (CH 3) = , etc. CH ₂ and the like.

Preferable specific examples of the monomer (B) include Chisso Silaplane TM-0701T, Chisso Silaplane FM-0711, Shin-Etsu Chemical X-22-2475, Shin-Etsu Chemical X-22 2426, Shin-Etsu Chemical X-22-174DX, Shin-Etsu Chemical KBM-5103, and the like.

Preferred specific examples of the monomer (C) include NOF BREMMER AE-400, NOF BLEMER AE-90, NOF BLEMER AP-400, NOF BLEMER PE-200, Examples include Blemmer 50PEP-300 manufactured by Oil Co., Ltd. and Blemmer 55PET-800 manufactured by NOF Corporation.

Preferable specific examples of the monomer (D) include 2- (isocyanatoethyl) methacrylate, 2- (isocyanatoethyl) acrylate, acrylic acid, methacrylic acid, 2-acryloyloxyethylphthalic acid and the like.

Examples of the monomer-containing (B) silicone-containing (meth) acrylate include those represented by the following formula.

[Wherein, R ¹ represents H or CH ₃ , R ² represents a divalent alkylene group having 1 to 10 carbon atoms, an alkylene oxide group, or a divalent arylene group which may have a substituent, Y represents a single bond, an ester bond (—COO— or —O—CO—), an amide bond (—CONH— or —NHCO—), a sulfonate ester bond (—SO ₂ —O— or —O—SO ₂ —). ), Sulfonamide bond (—SO ₂ NH— or —NHSO ₂ —), ether bond (—O—) or thioether bond (—S—), and R ³ , R ⁴ , and R ⁵ are the same or different. Each is H or an alkyl group having 1 to 8 carbon atoms or

(R ⁷ to R ⁹ each represents H or an alkyl group having 1 to 8 carbon atoms, and may be linear, branched or cyclic. These alkyl groups may have a substituent. The substituent is not particularly limited as long as it does not adversely affect the present invention.

P is an integer of 1 or more, for example, an integer of 1-20, 1-15, 1-10, 1-5, 4, 3, 2, or 1.

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

The (meth) acrylate of the monomer (C) is a (meth) acrylate that does not contain fluorine and silicone, and is particularly preferably an alkylene oxide-containing (meth) acrylate, specifically represented by the following formula: It is characterized by.

In the formula, R ¹ represents H or CH ₃ .

In the formula, AO represents a divalent alkylene oxide having 2 to 4 carbon atoms, and the group represented by — (AO) n— represents an alkylene oxide having 2 to 4 carbon atoms (for example, —CH ₂ CH ₂ O—, _{-CH (CH 3) CH 2 O} -, - CH 2 CH 2 CH 2 O -, - CH 2 CH 2 CH 2 CH 2 O-), 1 or more kinds of polymers (two or more heavy of In the case of a coalescence, it may be polymerized in block form or in random form).

In the formula, n represents the average number of added moles and represents an integer of n = 2 to 20.

In the formula, W represents a functional group such as an alkoxyl group, an aryl group which may have a substituent, a hydroxyl group, a carboxy group, an amino group, or a mercapto group.

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

The compound (D) having a reactive functional group is represented by the following formula, for example, an isocyanate group-containing (meth) acrylate, a glycidyl group-containing (meth) acrylate, an oxetane-containing (meth) acrylate, and a lactone Examples thereof include ring-containing (meth) acrylate and phosphate group-containing (meth) acrylate.

In the formula, R ¹ represents H or CH ₃ .

In the formula, R ⁶ is a divalent alkylene group having 1 to 10 carbon atoms, an alkylene oxide group (—O— (alkylene having 1 to 10 carbon atoms)) or a divalent arylene group which may have a substituent. (Phenylene, naphthylene, etc.). The alkylene group of the “C 1-10 divalent alkylene group” may be linear, branched or cyclic. Examples thereof include a methylene group, an ethylene group, a propylene group, a butylene group, a cyclopentylene group, a cyclohexylene group, and an octylene group. These alkylene groups may have a substituent, and the substituent is not particularly limited as long as it does not adversely affect the present invention. Examples of the substituent include an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and a halogen group.

In the formula, W ¹ is not particularly limited as long as it is a functional group that reacts with W, and examples thereof include an isocyanate group, a glycidyl group, an oxetane group, a lactone group, and a phosphoric acid group.

In addition, the compound (D) may be used singly or in combination of two or more.

Method of Use Copolymers of the monomers (A) to (C) and a copolymer obtained by addition polymerization of the compound (D) are, for example, toluene, xylene, diethyl ether, ethyl acetate, methyl ethyl ketone, acetone, acetonitrile , Solutions of organic solvents such as propionitrile, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, ethanol, isopropanol, tetrahydrofuran, 1,4-dioxane, or solutions added to coating liquids (resin compositions) such as paints Can be used as

A copolymer obtained by polymerizing the monomers (A) to (C) and, if necessary, the compound (D) (hereinafter sometimes referred to as “fluorinated silicone copolymer”) is a single type. It may be used in a mixture of two or more. Moreover, the said solvent used for this solution may be used individually by 1 type, and 2 or more types may be mixed and used for it.

The solution containing the fluorine-containing silicone copolymer of the present invention is applied to the surface of a substrate such as a resin, film, fiber, glass, or metal by coating, coating, spraying, etc. It can be modified. That is, when the solvent in the solution evaporates, a film containing the fluorine-containing silicone copolymer of the present invention is formed on the substrate surface. The film has water / oil repellency, antifouling property, leveling property, slipperiness and the like. The drying (evaporation) conditions of the solvent vary depending on the type and amount of the solvent in the solution, but are usually dried at room temperature to 200 ° C. for about 10 seconds to 10 minutes.

Since the fluorine-containing silicone copolymer of the present invention can have a reactive acrylate group or a methacrylate group in the molecule, it has a high surface modification effect due to enhanced adhesion using a chemical bond to the substrate surface. Can be expected. That is, the acrylic group or methacryl group which is a reactive group in the copolymer of the present invention reacts with the substrate surface and / or the fluorine-containing silicone copolymer itself, usually by light. The photoreaction varies depending on the conditions and cannot be limited. However, it can usually be achieved by irradiating light having a wavelength of about 250 nm to 400 nm with 100 to 500 mJ / cm ² . The photoreaction may be performed after the drying treatment. The photoreaction can also use sunlight in some cases. Thereby, the film | membrane of a fluorine-containing silicone copolymer adheres on the base-material surface, and high sustainability, such as water / oil repellency, antifouling property, leveling property, and slipperiness, is achieved.

Further, by controlling the amount of reactive groups in the copolymer molecule, reaction conditions, etc., it is possible to improve the film strength as a surface modifier and to design the strength according to the purpose.

The concentration of the fluorine-containing silicone copolymer solution in the solution is not particularly limited, but may be, for example, about 0.1 to 90.0% by mass. If the concentration of the fluorinated silicone copolymer solution in the solution is too low, the amount of the fluorinated silicone copolymer present on the surface will be reduced, and the coated or sprayed modified surface will become thinner or reactive. It becomes a factor of decline. In addition, problems such as insufficient strength of the modified surface may occur. On the other hand, if the concentration is too high, uneven coating may occur. The concentration of the fluorine-containing silicone copolymer solution in the solution is also affected by the solubility depending on the type of solvent and the molecular weight of the polymer.

Resin Composition Containing Fluorine-Containing Silicone Copolymer as Active Component The curable resin composition included in the present invention is prepared as a coating liquid for application to a substrate. In the curable resin composition (coating liquid), a fluorine-containing silicone copolymer is mainly used as a component that exhibits antifouling properties, an energy ray-curable resin monomer or resin oligomer that mainly functions as a resin film, and other polymerization starts. An agent, a solvent, etc. are blended. However, no solvent is blended in the case of a solvent-free coating solution, and no polymerization initiator is required in the case of radiation curing. Moreover, you may add another component to a coating liquid as needed.

The monomers (A) to (C) in the total amount of the curable resin composition of the present invention (excluding the amount of the solvent component when a solvent component is used) and the compound (D) as an optional component are polymerized. The content of the fluorine-containing silicone copolymer is usually about 0.0006 to 17% by mass, preferably about 0.007 to 13% by mass, and more preferably about 0.07 to 10% by mass.

The fluorine-containing silicone copolymer of the present invention exhibits a function as an antifouling agent in a cured film obtained by polymerization with an energy ray curable resin monomer and / or a resin oligomer described later.

Energy-ray curable resin monomer or resin oligomer component The curable resin composition of the present invention comprises, in addition to the fluorine-containing silicone copolymer, an energy-ray curable resin monomer and / or resin that reacts with this to form a resin-cured film. Includes oligomers (hereinafter sometimes referred to as resin monomers and resin oligomers).

Such a resin monomer and resin oligomer are not particularly limited as long as they form a cured film by reacting with a fluorine-containing silicone copolymer, and are usually energy ray cured used for a hard coat film or an antireflection coat film. Resin monomers and / or resin oligomers can be optionally used.

Examples of the resin monomer and resin oligomer include acrylic, urethane, epoxy, and silicone reactive compounds such as various acrylates and acrylic urethanes, and acrylic resins are preferably used. In particular, since the curable resin composition of the present invention is cured and used in the form of a film, it is preferable to use a resin monomer and / or a resin oligomer having a bifunctional or higher functional group.

Examples of resin monomers and resin oligomers having a bifunctional or higher reactive functional group include tricyclodecane dimethylol diacrylate, bisphenol F EO-modified diacrylate, bisphenol A EO-modified diacrylate, isocyanuric acid EO-modified diacrylate, and polypropylene. Glycol diacrylate, polyethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, trimethylolpropane PO-modified triacrylate, glycerin PO-added triacrylate, trimethylolpropane EO-modified triacrylate, trimethylolpropane EO-modified trimethacrylate , Isocyanuric acid EO-modified diacrylate, isocyanuric acid EO-modified triacrylate, ε- Prolactone-modified tris (acryloxyethyl) isocyanurate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, various urethane acrylate oligomers Shigumi series manufactured by company, Art Resin series manufactured by Negami Kogyo Co., Ltd., etc.), and the like. The resin monomer and resin oligomer may be used alone or in combination of two or more at any ratio.

Examples of energy rays for curing resin monomers and resin oligomers include radiation, electron beams, ultraviolet rays, and visible rays. Since the energy of electromagnetic waves is high in curing with radiation and electron beam, polymerization is possible only with a polymerizable double bond. When ultraviolet rays and visible rays are used as energy sources, it is preferable to blend a polymerization initiator component described later.

The content of the resin monomer and resin oligomer in the total amount of the curable resin composition of the present invention (excluding the amount of the solvent component when a solvent component is used) is usually about 55 to 99.9% by mass, preferably Is about 60 to 99.5% by mass, and more preferably about 70 to 99% by mass.

The ratio of the resin monomer and resin oligomer to the fluorine-containing silicone copolymer used is usually about 0.001 to 18 parts by mass of the fluorine-containing silicone copolymer with respect to 100 parts by mass of the resin monomer and resin oligomer. The amount is preferably about 0.01 to 15 parts by mass, more preferably about 0.1 to 10 parts by mass.

Polymerization initiator component In addition to the said fluorine-containing silicone copolymer, a resin monomer, and / or a resin oligomer, the curable resin composition of this invention may contain the polymerization initiator component as needed.

A conventionally well-known thing can be used for a polymerization initiator component, For example, a photoinitiator can be used.

A wide variety of photopolymerization initiators are known and may be selected as appropriate. For example, 1-hydroxy-cyclohexyl-phenyl ketone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, benzophenone, 1- [4- (2-hydroxyethoxy-phenyl) -2-hydroxy-2-methyl-1-propan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane- 1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-benzylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2-hydroxy-1- {4- [4- (2-hydroxy -2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propan-1-one, 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], Ethanone, [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (0-acetyloxime), 2,2-bis (2-chlorophenyl) -4,4 5,5-tetraphenyl-1,2-biimidazole, 2,2-diethoxyacetophenone, benzophenone, methyl O-benzoylbenzoate, 4,4-bis (dimethylamino) benzophenone, dibenzyl ketone, fluorenone, 2- Hydroxy-2-methylpropiophenone, thioxanthone, benzyldimethylketanol, benzylmethoxyethyl acetal, benzo In, anthraquinone, anthrone, dibenzosuberone, 4,4-bis (dimethylamino) chalcone, P-dimethylaminocinnamylidene indanone, 2- (P-dimethylaminophenylvinylene) -isonaphthothiazole, 3,3- Examples thereof include carbonyl-bis (7-diethylaminocoumarin), 3-phenyl-5-benzoylthio-tetrazole and the like.

When the polymerization initiator component is used, one type can be used alone, but two or more types may be arbitrarily blended and used. The addition amount of the polymerization initiator component is usually about 0.1 to 50 parts by mass with respect to 100 parts by mass of the polymerizable resin component (the total amount of the fluorine-containing silicone copolymer, the resin monomer and / or the resin oligomer), The amount is preferably about 0.5 to 40 parts by mass, more preferably about 1 to 30 parts by mass.

Solvent component The curable resin composition of the present invention need not contain a solvent component, but may contain a solvent component as necessary. As the solvent component, conventionally known solvent components may be used, and examples thereof include alcohols such as methanol, ethanol and isopropyl alcohol, ketones such as acetone and methyl ethyl ketone, and esters such as ethyl acetate and butyl acetate. These solvent components can be used alone or in combination of two or more at any ratio.

When the solvent component is used, the amount of the solvent component in the curable resin composition of the present invention is 100 polymerizable resin components (total amount of the pre-fluorinated silicone copolymer, the resin monomer and / or the resin oligomer). The amount is usually about 25 to 5000 parts by mass, preferably about 40 to 2000 parts by mass, and more preferably about 60 to 1000 parts by mass with respect to parts by mass.

Other Components The curable resin composition of the present invention may contain fine particles, fillers and the like as necessary in order to provide a shape on the surface of the cured film and to provide other desired functions.

Method for Producing Cured Film In the present invention, the curable resin composition of the present invention is used as a coating liquid, and after the coating liquid is applied to a substrate, a cured film can be formed by light irradiation or the like.

As a procedure for obtaining the cured film of the present invention, a fluorine-containing silicone copolymer represented by the monomers (A) to (C) and the compound (D), a resin monomer and / or a resin oligomer, If necessary, the curable resin composition of the present invention is prepared as a coating liquid by mixing and dissolving a polymerization initiator component, a solvent component, fine particles, a filler and the like at an appropriate blending ratio. Next, the coating liquid is applied on the substrate so as to have a certain film thickness, and after removing the solvent component by hot air drying, vacuum drying, etc., irradiation with energy rays such as radiation, electron beams, ultraviolet rays, and visible rays is performed. Thus, a cured film can be obtained.

The coating method of the coating liquid is not particularly limited, but for example, it is applied by wet coating, and as its method, for example, gravure method, bar coating method, wire bar method, spin coating method, doctor blade method, dip coating method, slit coating method Etc.

The substrate for producing the cured film is not particularly limited as long as the cured film can be supported, but for example, a transparent sheet is desirable when used as a hard coat for optical applications. Examples of the material for the transparent sheet include glass and plastic, and a plastic sheet is particularly preferable. As the plastic, thermoplastic resins, thermosetting resins and the like can be used, for example, polyolefin resins such as polyethylene and polypropylene, polyester resins such as polyethylene terephthalate, cellulose resins such as triacetyl cellulose and butyl cellulose, polystyrene resins, polyurethane resins, Examples thereof include polyvinyl alcohol, polyvinyl chloride, acrylic resin, polycarbonate resin, polyacrylonitrile, cycloolefin polymer, and polyethersulfone. These sheets may be subjected to an easy attachment process such as a binder process, a corona process, a plasma process, or a flame process, if necessary.

The thickness of the cured film of the present invention is not particularly limited, and may be appropriately selected depending on the application. Usually, it can be about 100 nm to 30 μm.

The contents of the present invention will be described with reference to the following examples, but the contents of the present invention should not be construed as being limited to the examples.

Synthesis example 1
In a three-necked flask (3 L) equipped with a dropping funnel, 259.5 g (1.8 mol) of 4-hydroxybutyl acrylate, 218.6 g (2.16 mol) of triethylamine, and 1000 g of acetonitrile were placed. The dropping funnel was charged with 973.0 g (2.16 mol) of hexafluoropropene trimer and gradually dropped into the solution in the flask over about 60 minutes with stirring. After completion of the dropwise addition, stirring was continued for another 3 hours at room temperature.

The reaction mixture was added with 2200 g of 1N hydrochloric acid to stop the reaction, and then the reaction mixture was transferred into a 5 L beaker, followed by washing with 1 L of water three times. The solution after the water washing treatment was dehydrated under reduced pressure to obtain 964.0 g (yield 93%) of a fluorinated acrylate represented by the following formula (A-1). Table 1 shows the ¹ H-NMR data of the obtained fluorinated acrylate (A-1).

[Wherein Rf is the following general formula

An isomer mixture of the group represented by ]

Synthesis example 2
In a three-necked flask (100 mL) equipped with a condenser tube, 2.87 g (5 mmol) of the fluorine-containing acrylate (A-1) synthesized in Synthesis Example 1, Silaplane TM-0701T (B-1) 2 manufactured by Chisso Corporation .11 g (5 mmol), NOF BLEMER AE-400 (C-1) 5.12 g (10 mmol), propylene glycol monomethyl ether acetate 10.10 g, 2,2′-azobisisobutyronitrile 0.10 g ( 0.6 mmol) and 0.27 g (1.3 mmol) of lauryl mercaptan. Nitrogen gas was introduced into the reaction solution, and the inside of the reaction vessel was purged with nitrogen. After nitrogen substitution, the reaction solution was heated to 90 ° C. while stirring the reaction solution to start the reaction. Thereafter, stirring was continued at 90 ° C. for 21 hours. The completion of the reaction was confirmed by disappearance of the peak specific to each acrylate in ¹ H-NMR. The objective fluorine-containing silicone copolymer was quantitatively obtained (50% by mass propylene glycol monomethyl ether acetate solution).

The weight average molecular weight of the obtained fluorine-containing silicone copolymer was confirmed using GPC. Table 3 shows the measurement results.

Synthesis example 3
Synthesis was carried out in the same procedure as in Synthesis Example 2 with the ratio of monomers (A-1), (B-1), and (C-1) changed. The weight average molecular weight of the obtained fluorine-containing silicone copolymer was confirmed using GPC. The monomer ratio and GPC measurement results are as shown in Table 3.

Synthesis example 4
Synthesis was carried out in the same procedure as in Synthesis Example 2 using Chisso Silaplane FM-0711 (B-2) instead of Monomer (B-1). The weight average molecular weight of the obtained fluorine-containing silicone copolymer was confirmed using GPC. The monomer ratio and GPC measurement results are as shown in Table 3.

Synthesis example 5
Synthesis was carried out in the same manner as in Synthesis Example 2 while changing the ratio of monomers (A-1), (B-2), and (C-1). The weight average molecular weight of the obtained fluorine-containing silicone copolymer was confirmed using GPC. The monomer ratio and GPC measurement results are as shown in Table 3.

Synthesis Example 6
In the same procedure as in Synthesis Example 2, instead of the monomer (A-1), a linear fluorine-containing acrylate (A-2: CF ₃ (CF ₂ ) ₅ CH ₂ CH ₂ OC (═O) CH═CH ₂ ) Was used for the synthesis. The weight average molecular weight of the obtained fluorine-containing silicone copolymer was confirmed using GPC. The monomer ratio and GPC measurement results are as shown in Table 3.

Synthesis example 7
Synthesis was carried out in the same procedure as in Synthesis Example 2 using Chisso Silaplane FM-0711 (B-2) instead of Monomer (B-1). The weight average molecular weight of the obtained fluorine-containing silicone copolymer was confirmed using GPC. The monomer ratio and GPC measurement results are as shown in Table 3.

Synthesis Example 8
Synthesis was carried out in the same procedure as in Synthesis Example 2 using (A-1) and (A-2) as monomers (A). The weight average molecular weight of the obtained fluorine-containing silicone copolymer was confirmed using GPC. The monomer ratio and GPC measurement results are as shown in Table 3.

Synthesis Example 9
Synthesis was performed in the same procedure as in Synthesis Example 11 using Chisso Silaplane FM-0711 (B-2) instead of Monomer (B-1). The weight average molecular weight of the obtained fluorine-containing silicone copolymer was confirmed using GPC. The monomer ratio and GPC measurement results are as shown in Table 3.

Synthesis Example 10
In a three-necked flask (3 L) equipped with a dropping funnel, 130.1 g (1.0 mol) of 2-hydroxyethyl methacrylate, 111.1 g (1.1 mol) of triethylamine, and 600 g of ethyl acetate were placed. In a dropping funnel, 586.5 g (1.0 mol) of a fluorine-containing acid chloride represented by the following formula (1) and 100 g of ethyl acetate were added and gradually dropped into the solution in the flask over about 60 minutes with stirring. After completion of the dropwise addition, stirring was continued for another 3 hours at room temperature.

The reaction mixture was added with 1050 g of 1N hydrochloric acid to stop the reaction, and then the reaction mixture was transferred into a 3 L beaker, and then washed with 1 L of water three times. The solution after the water washing treatment was dehydrated under reduced pressure to obtain 634.8 g (yield 93%) of fluorinated methacrylate represented by the following formula (A-3). Table 1 shows the ¹ H-NMR data of the resulting fluorinated methacrylate (A-3).

[Wherein Rf is the following general formula

It is group shown by these. ]

[Wherein Rf is the following general formula

It is group shown by these. ]

Synthesis Example 11
In the same procedure as in Synthesis Example 2, instead of the monomer (A-1), fluorine-containing methacrylate (A-3: RfOC ₆ H ₄ CO ₂ (CH ₂ ) ₂ OC (═O) C (CH ₃ ) = The synthesis was carried out using X-22-174DX (B-3) manufactured by Shin-Etsu Chemical Co., Ltd. instead of CH ₂ ) and monomer (B-1). The weight average molecular weight of the obtained fluorine-containing silicone copolymer was confirmed using GPC. The monomer ratio and GPC measurement results are as shown in Table 3.

In the obtained fluorine-containing silicone copolymer, 0.5 equivalent of monomer (D-1: 2- (isocyanatoethyl) methacrylate) and 0.01 equivalent of equivalent to monomer (C-1) 1,4-diazabicyclo [2.2.2] octane was added and stirring of the reaction solution was continued at 50 ° C. for 12 hours. The completion of the reaction was confirmed by disappearance of —N═C═O absorption (2275-2250 cm ⁻¹ ) using FT-IR.

Synthesis Comparative Example 1
Synthesis was carried out in the same procedure as in Synthesis Example 2, except that the monomer (B-1) was not added and ethyl acetate was used instead of propylene glycol monomethyl ether acetate. The weight average molecular weight of the obtained fluorine-containing copolymer (silicone-free) was confirmed using GPC. The monomer ratio and GPC measurement results are as shown in Table 3.

Synthesis Comparative Example 2
Synthesis was carried out in the same procedure as in Synthesis Example 2 without adding the monomer (A-1). The weight average molecular weight of the obtained silicone-containing copolymer (containing no fluorine) was confirmed using GPC. The monomer ratio and GPC measurement results are as shown in Table 3.

Synthesis Comparative Example 3
Synthesis was carried out in the same procedure as in Synthesis Example 2 without adding the monomer (A-1). The weight average molecular weight of the obtained silicone-containing copolymer (containing no fluorine) was confirmed using GPC. The monomer ratio and GPC measurement results are as shown in Table 3.

Synthesis Comparative Example 4
Synthesis was carried out in the same procedure as in Synthesis Example 2 with the ratio of monomers (A-1), (B-1), and (C-1) changed. The weight average molecular weight of the obtained fluorine-containing silicone copolymer was confirmed using GPC. The monomer ratio and GPC measurement results are as shown in Table 3.

Synthesis Comparative Example 5
Synthesis was carried out in the same manner as in Synthesis Example 2 while changing the ratio of monomers (A-1), (B-2), and (C-1). The weight average molecular weight of the obtained fluorine-containing silicone copolymer was confirmed using GPC. The monomer ratio and GPC measurement results are as shown in Table 3.

Examples 1 to 13
0.04 part by mass (50% by mass solution product) of the fluorine-containing silicone copolymer described in Synthesis Examples 2 to 9 and 11 or the copolymer described in Synthesis Comparative Examples 1 to 5 and 20 parts by mass of phenol resin In addition to propylene glycol monomethyl ether acetate, a glass plate (100 mm × 100 mm × 2 mm, used after degreasing acetone) was coated with a spin coater (1H07 manufactured by Mikasa). Then, it was dried at 100 ° C. for 90 seconds. The surface condition was confirmed, and the contact angles of water and hexadecane were measured using a DropMaster 700 manufactured by Kyowa Interface Science Co., Ltd. The measurement results are shown in Table 4.

Example 14
Without adding a fluorine-containing silicone copolymer, 20 parts by mass of a phenolic resin is added to propylene glycol monomethyl ether acetate, and a spin coater (1H07 made by Mikasa) is used on a glass plate (100 mm × 100 mm × 2 mm, used after degreasing acetone). The coating process was performed. Then, it was dried at 100 ° C. for 90 seconds. The surface condition was confirmed, and the contact angles of water and hexadecane were measured using a DropMaster 700 manufactured by Kyowa Interface Science Co., Ltd. The measurement results are shown in Table 4.

Examples 15-28
20 parts by mass of pentaerythritol tri / tetraacrylate (manufactured by Nichia Gosei Co., Ltd., trade name: M-305) as a curable resin monomer, 1-hydroxy-cyclohexyl-phenyl-ketone (Ciba Specialty Chemicals) as a photopolymerization initiator Product, trade name: Irgacure 184), 0.4 parts by mass of the fluorine-containing silicone copolymer described in Synthesis Examples 2 to 9 and 11 or the copolymer described in Synthesis Comparative Examples 1 to 5 ( 50 wt% solution product) and 78.8 parts by mass of methyl ethyl ketone (MEK) as a solvent were mixed to prepare a curable coating solution. This was spread on a polyester film with a No. 8 bar coater, put into a drier set at 60 ° C. for 5 minutes to volatilize the solvent, and then irradiated with UV to obtain a cured film. Each evaluation result is shown in Table 5.

Example 29
No fluorine-containing silicone copolymer was added, 20 parts by mass of pentaerythritol tri / tetraacrylate (manufactured by Nichia Gosei Co., Ltd., trade name: M-305) as a curable resin monomer, and 1-hydroxy-cyclohexyl as a photopolymerization initiator -Phenyl-ketone (manufactured by Ciba Specialty Chemicals, trade name: Irgacure 184) was mixed with 0.8 part by mass, and 78.8 parts by mass of methyl ethyl ketone (MEK) as a solvent was mixed to prepare a curable coating solution. . This was spread on a polyester film with a No. 8 bar coater, put into a drier set at 60 ° C. for 5 minutes to volatilize the solvent, and then irradiated with UV to obtain a cured film. Each evaluation result is shown in Table 5.

Examples 30-43
30 parts by mass of urethane acrylate as a curable resin monomer, 3 parts by mass of 1-hydroxy-cyclohexyl-phenyl-ketone (trade name: Irgacure 184, manufactured by Ciba Specialty Chemicals) as a photopolymerization initiator, Synthesis Examples 2 to 9 And 11 or 0.6 parts by mass (50 mass% solution product) of the copolymer described in Synthesis Comparative Examples 1 to 5, and 66.4 mass% of methyl isobutyl ketone (MIBK) as a solvent. Parts were mixed to prepare a curable coating solution. This was spread on a polyester film with a No. 8 bar coater, put into a dryer set at 100 ° C. for 10 minutes, the solvent was volatilized, and then irradiated with UV to obtain a cured film. Each evaluation result is shown in Table 6.

Example 44
No fluorine-containing silicone copolymer was added, 30 parts by mass of urethane acrylate as a curable resin monomer, and 1-hydroxy-cyclohexyl-phenyl-ketone (produced by Ciba Specialty Chemicals, Inc., trade name: Irgacure 184) as a photopolymerization initiator ) And 66.4 parts by mass of methyl isobutyl ketone (MIBK) as a solvent were mixed to prepare a curable coating solution. This was spread on a polyester film with a No. 8 bar coater, put into a dryer set at 100 ° C. for 10 minutes, the solvent was volatilized, and then irradiated with UV to obtain a cured film. Each evaluation result is shown in Table 6.

Evaluation (1) Leveling I
The coated surface was visually observed.
Evaluation criteria: No striation = ○
There is a striation ＝ ×

(2) Leveling II
The cured film surface after UV irradiation was visually observed.
Evaluation criteria: No streak, repelling, etc. = ○
There are streaks, repellents, etc. = ×

(3) Compatibility The compatibility of the curable coating solution was visually observed.
Evaluation criteria: Transparent = ○
Cloudiness = ×

(4) Water repellency I
The contact angle of water with the cured film surface immediately after production was measured with a contact angle measurement device (DropMaster 600 manufactured by Kyowa Interface Chemical).
Evaluation criteria: Water contact angle of 80 degrees or more = ○
Water contact angle is 80 degrees or less = ×

(5) Water repellency II
The contact angle of water with the cured film surface immediately after production was measured with a contact angle measurement device (DropMaster 600 manufactured by Kyowa Interface Chemical).
Evaluation criteria: Water contact angle is 95 degrees or more = ○
Water contact angle is 95 degrees or less = ×

(6) Oil repellency I
The contact angle of hexadecane to the cured film surface immediately after production was measured with a contact angle measuring device (DropMaster 600 manufactured by Kyowa Interface Chemical).
Evaluation criteria: Hexadecane contact angle is 20 degrees or more = ○
The contact angle of hexadecane is 20 degrees or less = ×

(7) Oil repellency II
The contact angle of hexadecane to the cured film surface immediately after production was measured with a contact angle measuring device (DropMaster 600 manufactured by Kyowa Interface Chemical).
Evaluation criteria: Hexadecane contact angle is 30 degrees or more = ○
The contact angle of hexadecane is 30 degrees or less = ×

(8) Antifouling property I
Fingerprints were attached to the surface of the cured film, the fingerprints were wiped until they were no longer visible, and the number of times (one round trip) was counted.
Evaluation criteria: Number of times of wiping <Blank = ○
Number of wipes ≥ Blank or Cannot be wiped = ×

(9) Antifouling II
Random lines were drawn on the surface of the cured film with oil-based magic, and it was visually confirmed whether the magic could be wiped off.
Evaluation criteria: Oily magic can be wiped off
Oil-based magic cannot be wiped off

(10) Ease of slip The slipperiness of the cured film surface was evaluated in three stages.
Evaluation criteria: 3 Slip well 2 Slip (no resistance)
1 Non-slip (with resistance)

As can be seen from Table 4, striation can be suppressed by adding an additive, and water / oil repellency is improved by adding a fluorine-containing silicone copolymer.

As can be seen from Tables 5 and 6, even if the resin is changed, streaks and repellency can be suppressed by adding an additive, and the addition of a fluorine-containing silicone copolymer improves the water and oil repellency. Further, the fluorine-containing copolymer and the fluorine-containing silicone copolymer having a small proportion of the silicone-containing (meth) acrylate have insufficient magic wiping performance, and the silicone-containing copolymer has insufficient fingerprint wiping performance. In the fluorine-containing silicone copolymers of 9 and 11, fingerprint wiping performance and magic wiping performance are improved.

The fluorine-containing silicone copolymer according to the present invention is useful as a surface modifier for imparting antifouling properties used in the fields of glass, fibers, metals, resins, films, optical materials, paints and the like. It is useful as a compound that can impart smoothness, water / oil repellency and antifouling properties to the surface of the material.

Claims (11)

1. Antifouling property-imparting agent containing (meth) acrylate copolymer containing the following monomer (A), monomer (B), and monomer (C) as a copolymerization component:
   Monomer (A): Fluorine-containing (meth) acrylate
   

   

   [Wherein, Rf represents a perfluoroalkyl group or a perfluoroalkenyl group having 1 to 9 carbon atoms, R ¹ represents H or CH ₃ , and R ² represents a divalent saturated fat having 1 to 50 carbon atoms. Aromatic hydrocarbon group (the divalent saturated aliphatic hydrocarbon group may be substituted with a halogen atom or an aryl group, and the divalent saturated aliphatic hydrocarbon group is an ether bond (—O—) , A thioether bond (—S—), an ester bond (—COO— or —O—CO—), an amide bond (—CONH— or —NHCO—) and an arylene group. And Y is a single bond, ester bond (—COO— or —O—CO—), amide bond (—CONH— or —NHCO—), sulfonate bond (— S ₂ -O- or _-O-SO 2 -), sulfonamide bond _(-SO 2 NH- or -NHSO ₂ -), indicating an ether bond (-O-) or a thioether bond (-S-). ]
   Monomer (B): Silicone-containing (meth) acrylate Monomer (C): (Meth) acrylate other than the above
2. The antifouling property imparting agent according to claim 1, wherein the copolymer is further added with a compound (D) having a reactive functional group.
3. When the monomer composition of the copolymer is 100% by mass of the entire copolymer, the monomer (A) is 1 to 50% by mass, the monomer (B) is 1 to 50% by mass, The antifouling property-imparting agent according to claim 1, wherein the monomer (C) is 1 to 90% by mass and the monomer ratio is (B) / (A)> 0.3.
4. When the monomer composition of the copolymer is 100% by mass of the entire copolymer, the monomer (A) is 1 to 50% by mass, the monomer (B) is 1 to 50% by mass, The body (C) is 1 to 90% by mass, the compound (D) having a reactive functional group is 0 to 50% by mass, and the monomer ratio is (B) / (A)> 0.3. The antifouling property-imparting agent according to claim 2.
5. 2. The antifouling property according to claim 1, wherein Rf of the monomer (A) is a mixture of (meth) acrylate (A1) having a perfluoroalkyl group and (meth) acrylate (A2) having a perfluoroalkenyl group. Agent.
6. The antifouling property-imparting agent according to claim 1, wherein Rf of the monomer (A) is a perfluoroalkenyl group having up to 9 carbon atoms represented by the following formula.
   

   
7. The antifouling property-imparting agent according to claim 1, wherein the monomer (B) is a silicone-containing (meth) acrylate represented by the following formula.
   

   

   [Wherein R ¹ represents H or CH ₃ , R ² represents a divalent alkylene group having 1 to 10 carbon atoms, an alkylene oxide group or a divalent arylene group which may have a substituent, Y is a single bond, an ester bond (—COO— or —O—CO—), an amide bond (—CONH— or —NHCO—), a sulfonate ester bond (—SO ₂ —O— or —O—SO ₂ —). ), Sulfonamide bond (—SO ₂ NH— or —NHSO ₂ —), ether bond (—O—) or thioether bond (—S—), and R ³ , R ⁴ , and R ⁵ are the same or different. Each is H or an alkyl group having 1 to 8 carbon atoms or
   

   

   (R ⁷ to R ⁹ are each H or an alkyl group having 1 to 8 carbon atoms, and p is an integer of 1 or more). ]
8. Monomer (C) is an alkylene oxide-containing (meth) acrylate represented by the following formula
   

   

   [Wherein, R ¹ represents H or CH ₃ , AO represents a divalent alkylene oxide having 2 to 4 carbon atoms, and the group represented by — (AO) n— represents an alkylene having 2 to 4 carbon atoms] 1 or 2 or more types of polymers of oxides (in the case of polymers of 2 or more types of alkylene oxides, each alkylene oxide may be polymerized in block form or randomly), and n 2 represents an integer of 2 to 20, and W represents an alkoxy group, an aryl group which may have a substituent, a hydroxyl group, a carboxy group (COOH), an amino group, or a mercapto group. Antifouling agent.
9. The antifouling property-imparting agent according to claim 2, wherein the compound (D) having a reactive functional group is a (meth) acrylate having a functional group (W ¹ ) represented by the following formula.
   

   

   [Wherein, R ¹ represents H or CH ₃ , R ⁶ represents an alkylene group or a divalent arylene group which may have a substituent, and W ¹ represents an isocyanate group, a glycidyl group, an oxetane group, a lactone, Group or phosphate group]
10. An antifouling resin composition comprising the antifouling property-imparting agent according to any one of claims 1 to 9 and a resin.
11. The antifouling resin composition according to claim 10, wherein the resin is an energy curable type or a thermosetting type.