JP2011213818A - Fluorine-containing curable resin and active energy ray curable coating composition using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a fluorine-containing curable resin which provides a cured coating film surface with an excellent antifouling property and can be used as a fluorine-based surfactant, and to provide an active energy ray curable coating composition which can prevent the volatilization or separation of the fluorine-based surfactant or a decomposed product thereof from the cured coating film surface due to heat treatment or the like after coating and curing, and gives a highly stable excellent antifouling property after stains adhered on the cured coating film surface are removed, and to provide a cured product of the composition and an article having the cured coating film.SOLUTION: There are provided the fluorine-containing curable resin including a polymer having a poly(perfluoroalkylene ether) chain, a polyalkylene ether chain and a radical polymerizable unsaturated group in the structure of the polymer, and an active energy ray curable coating composition incorporated with the fluorine-containing curable resin.

Description

  The present invention relates to a fluorine-containing curable resin that can impart excellent antifouling properties to the surface of a cured coating film and can be used as a fluorine-based surfactant or a fluorine-based surface modifier. The present invention also relates to an active energy ray-curable coating composition using the fluorine-containing curable resin, a cured product thereof, and an article having the cured coating film.

  Fluorine-based surfactants or fluorine-based surface modifiers are excellent in leveling, wettability, permeability, anti-blocking, slipperiness, water / oil repellency, antifouling properties, etc. Widely used in quality materials.

  A cured coating obtained by applying and curing an active energy ray-curable coating containing this fluorosurfactant or fluorochemical surface modifier (hereinafter simply referred to as “fluorosurfactant”). While the film exhibits excellent antifouling properties, a part of the fluorosurfactant is cured and coated by heating, humidification, exposure to chemicals such as acid and alkali, washing and wiping to remove dirt, etc. There was a problem that the antifouling property on the surface of the cured coating film was lowered due to desorption or volatilization from the film surface.

  For example, in the field of coating materials for protective films such as triacetyl cellulose (TAC) films in polarizing plates for liquid crystal displays, a fluorosurfactant is added to provide antifouling properties against fingerprints and dirt on the film surface. An ultraviolet curable hard coat material is coated on the surface of the protective film. However, there has been a problem that the antifouling property after removing the dirt adhering to the coated film surface by wiping or the like is greatly reduced.

  Therefore, in order to prevent such a decrease in the antifouling property on the surface of the cured coating film, a monoacrylate having a fluorinated alkyl group was copolymerized with an acrylic monomer having active hydrogen, and then obtained. A polymerizable fluorosurfactant having an unsaturated group obtained by reacting an acrylic monomer having an isocyanate group with a polymer has been proposed (for example, see Patent Document 1). This polymerizable fluorosurfactant has a polymerizable group, and is covalently bonded to the polymerization component in the active energy ray-curable coating composition and fixed to the coating film, so that it is stable to a certain extent. However, there is a problem that the antifouling property after removing dirt adhering to the surface of the coating film by wiping or the like is lowered, and sufficient antifouling property cannot be exhibited.

  In addition, a perfluoropolyether group-containing urethane acrylate obtained by reacting a hydroxyl group-containing perfluoropolyether and a hydroxyl group-containing acrylic monomer with a triisocyanate compound that is a diisocyanate trimer is used as a fluorosurfactant. It has been proposed (see, for example, Patent Document 2). In this perfluoropolyether group-containing urethane acrylate, it is difficult to react a hydroxyl group-containing perfluoropolyether and a hydroxyl group-containing acrylic monomer at an appropriate ratio with respect to a trifunctional isocyanate compound. Since a large amount of a compound having only a polyether or a compound having only an acryloyl group is produced, it was difficult to produce industrially.

JP 2007-246696 A Japanese Patent No. 3963169

  The problem to be solved by the present invention is to provide a fluorine-containing curable resin that can impart excellent antifouling properties to the surface of a cured coating film and can be used as a fluorine-based surfactant. In addition, it can prevent volatilization and detachment of the fluorosurfactant or its decomposition products from the surface of the cured coating film by heat treatment after application and curing, and removes dirt adhering to the surface of the cured coating film. It is to provide an active energy ray-curable coating composition that is highly stable and can impart excellent antifouling properties, a cured product thereof, and an article having the cured coating film.

  As a result of intensive studies to solve the above problems, the present inventors have found that a polymer having a poly (perfluoroalkylene ether) chain, a polyalkylene ether chain and a radically polymerizable unsaturated group in the resin structure, The active energy ray-curable coating composition containing a polymer has been found to exhibit excellent antifouling properties with high stability even after removal of dirt adhering to the surface of the cured coating film, and has completed the present invention. .

  That is, the present invention is a fluorine-containing curable resin characterized by being a polymer having a poly (perfluoroalkylene ether) chain, a polyalkylene ether chain and a radically polymerizable unsaturated group in the structure of the polymer, The present invention relates to an active energy ray-curable coating composition containing a fluorine-containing curable resin.

  Furthermore, the present invention provides a cured product obtained by applying the fluorine-containing curable resin or the active energy ray-curable coating composition to a substrate and irradiating and curing the active energy ray, and the fluorine-containing curable resin or An article having a cured coating film of an active energy ray-curable coating composition is provided.

  Since the fluorine-containing curable resin of the present invention has a radical polymerizable unsaturated group and has curability, it is antifouling on the surface of the base material by applying it to the base material alone to form a cured coating film. Can be granted. Moreover, after removing the stain | pollution | contamination adhering to the cured coating film surface, it exhibits high antifouling property with high stability. Furthermore, an active energy ray-curable coating composition containing the fluorine-containing curable resin as a fluorine-based surfactant has a difference in polarity with other atoms of fluorine atoms when applied to a substrate. The fluorine curable resin segregates on the surface of the coating film, and surface modification is possible by imparting antifouling property or the like only to the coating film surface. In addition, since the fluorine-containing curable resin has curability, it can be polymerized with other curable components in the active energy ray-curable coating composition, so that the fluorine-containing curing of the present invention is contained in the cured coating film. Resin is firmly fixed. Therefore, even if the cured coating is subjected to heat treatment or the like, it is possible to prevent volatilization or detachment of the fluorinated curable resin or its decomposition product from the surface of the cured coating. Dirty can be imparted.

  Therefore, the fluorine-containing curable resin of the present invention and the active energy ray-curable coating composition containing the same impart antifouling property to the surface of an article on which dirt such as fingerprints adheres, and the antifouling property is soiled. Since it persists at a high level after removal, it is optimal for imparting antifouling properties to the surface of articles that frequently repeat soiling and soiling removal.

FIG. 1 is an IR spectrum chart of the fluorinated curable resin (1) obtained in Example 1. 2 is a chart of the ¹³ C-NMR spectrum of the fluorinated curable resin (1) obtained in Example 1. FIG. FIG. 3 is a GPC chart of the fluorinated curable resin (1) obtained in Example 1.

  The fluorine-containing curable resin of the present invention is a fluorine-containing polymer having a poly (perfluoroalkylene ether) chain, a polyalkylene ether chain and a radically polymerizable unsaturated group in the structure of the polymer.

  The fluorine-containing curable resin of the present invention can be produced, for example, by the following four methods.

(Manufacturing method 1)
A poly (perfluoroalkylene ether) chain and a compound (A) having a radical polymerizable unsaturated group at both ends thereof, and a radical polymerizable unsaturated monomer having a polyalkylene ether chain (b1) and a reactive functional group (b2). The polymer (P1) obtained by copolymerizing the monomer (B1) as an essential monomer component has a functional group (c) reactive with the functional group (b2) and a radical polymerizable non-polymerizable component. A method of reacting a compound (C) having a saturated group.

(Manufacturing method 2)
Reaction between a poly (perfluoroalkylene ether) chain and a compound (A) having a radically polymerizable unsaturated group at both ends thereof, and a radically polymerizable unsaturated monomer (B2) having a polyalkylene ether chain (b1) A polymer (P2) obtained by copolymerizing a radically polymerizable unsaturated monomer (B3) having a functional functional group (b2) as an essential monomer component with respect to the functional group (b2) A method of reacting a reactive functional group (c) and a compound (C) having a radically polymerizable unsaturated group.

(Manufacturing method 3)
A polymer (P3) of a radically polymerizable unsaturated monomer (B3) having a reactive functional group (b2), a poly (perfluoroalkylene ether) chain and the reactive functional group (b2) at both ends thereof A compound (A ′) having a functional group (a) having reactivity with the polyalkylene ether chain (b1), a functional group (b3) having reactivity with the reactive functional group (b2), and a radical Compound (B4) having a polymerizable unsaturated group is reacted, and if necessary, a compound having a functional group (c) and a radically polymerizable unsaturated group having reactivity with respect to the functional group (b2) ( A method of reacting C).

(Manufacturing method 4)
A polymer (P3) of a radically polymerizable unsaturated monomer (B3) having a reactive functional group (b2), a poly (perfluoroalkylene ether) chain and the reactive functional group (b2) at both ends thereof A compound (A ′) having a reactive functional group (a), and a functional group (b3) having reactivity with the polyalkylene ether chain (b1) and the reactive functional group (b2). A method of reacting the compound (B4) with the compound (C) having a functional group (c) having reactivity with the functional group (b2) and a radically polymerizable unsaturated group.

  Next, each raw material used for the manufacturing method of said fluorine-containing curable resin of this invention is demonstrated.

  In the above production methods 1 and 2, the poly (perfluoroalkylene ether) chain, which is a raw material for the fluorine-containing curable resin of the present invention, and the compound (A) having radically polymerizable unsaturated groups at both ends thereof will be described. Examples of the poly (perfluoroalkylene ether) chain of the compound (A) include those having a structure in which divalent fluorocarbon groups having 1 to 3 carbon atoms and oxygen atoms are alternately connected. The divalent fluorocarbon group having 1 to 3 carbon atoms may be one kind or a mixture of plural kinds. Specifically, those represented by the following structural formula (a1) may be used. Can be mentioned.

（上記構造式（ａ）中、Ｘは下記構造式（ａ１−１）〜（ａ１−５）であり、構造式（ａ１）中の全てのＸが同一構造のものであってもよいし、また、複数の構造がランダムに又はブロック状に存在していてもよい。また、ｎは繰り返し単位を表す１以上の整数である。）

(In the structural formula (a), X is the following structural formulas (a1-1) to (a1-5), and all X in the structural formula (a1) may have the same structure, In addition, a plurality of structures may be present randomly or in a block shape, and n is an integer of 1 or more representing a repeating unit.

  Among these, the perfluoromethylene structure represented by the structural formula (a1-1) and the structure in that the coating film surface has particularly good wiping properties and excellent antifouling properties. Those coexisting with the perfluoroethylene structure represented by the formula (a1-2) are particularly preferable. Here, the abundance ratio between the perfluoromethylene structure represented by the structural formula (a1-1) and the perfluoroethylene structure represented by the structural formula (a1-2) is a molar ratio [structure (a1- 1) / structure (a1-2)] is preferably 1/10 to 10/1 in terms of antifouling property, and the value of n in the structural formula 1 is in the range of 3 to 100 In particular, 6 to 70 is preferable.

  The poly (perfluoroalkylene ether) chain is a poly (perfluoroalkylene ether) chain 1 because it has excellent dirt wiping property and slipperiness and is easy to improve the solubility in a non-fluorinated curable resin composition. The total number of fluorine atoms contained in the book is preferably in the range of 18 to 200, more preferably in the range of 25 to 150.

  The following general formulas (a2-1) to (a2-6) may be mentioned as the compound before the radically polymerizable unsaturated group is introduced at both ends as the raw material of the compound (A). In the following structural formulas, “—PFPE—” represents the poly (perfluoroalkylene ether) chain.

  Examples of the radically polymerizable unsaturated group at both ends of the chain of the compound (A) include those having a radically polymerizable unsaturated group represented by the following structural formulas U-1 to U-4.

  Among these radically polymerizable unsaturated groups, the structural formula U-1 is particularly preferred because the compound (A) itself is easily available and manufactured, or is excellent in reactivity with the radically polymerizable unsaturated monomer described above. The acryloyloxy group represented by these, or the methacryloyloxy group represented by Structural formula U-2 is preferable.

  Among the compounds (A), those having the acryloyloxy group or methacryloyloxy group include those represented by the following structural formulas (A-1) to (A-10). In the following structural formulas, “—PFPE—” represents a poly (perfluoroalkylene ether) chain.

  Among these, the structural formulas (A-1), (A) are particularly easy because the industrial production of the compound (A) itself is easy, and the polymerization reaction when producing the polymer (P) is also easy. -2), (A-5), and those represented by (A-6) are preferred.

  In order to produce the compound (A), for example, a method obtained by dehydrochlorinating a (meth) acrylic acid chloride with respect to a compound having one hydroxyl group at both ends of a poly (perfluoroalkylene ether) chain. , A method obtained by dehydrating (meth) acrylic acid, a method obtained by urethanizing 2- (meth) acryloyloxyethyl isocyanate, a method obtained by esterifying itaconic anhydride, poly (perfluoroalkylene ether) ) A method obtained by esterifying 4-hydroxybutyl acrylate glycidyl ether to a compound having one carboxyl group at both ends of the chain, a method obtained by esterifying glycidyl methacrylate, poly (perfluoroalkylene) Ether) One isocyanate group at each end of the chain For the compound to include a method of reacting a 2-hydroxyethyl acrylamide. Among these, a method obtained by dehydrochlorinating (meth) acrylic acid chloride for a compound having one hydroxyl group at both ends of a poly (perfluoroalkylene ether) chain, and 2- (meth) acryloyl A method obtained by subjecting oxyethyl isocyanate to a urethanization reaction is particularly preferred in that it is easily obtained synthetically.

  In the present invention, “(meth) acrylate” refers to one or both of methacrylate and acrylate, and “(meth) acryloyl group” refers to one or both of methacryloyl group and acryloyl group. “Acrylic acid” refers to one or both of methacrylic acid and acrylic acid.

  The said monomer (B1) used as the raw material of the fluorine-containing curable resin of this invention in the said manufacturing method 1 is demonstrated. The polyalkylene ether chain (b1) of the monomer (B1) is an organic group that is a polyether obtained by ring-opening polymerization of alkylene oxide. Examples of the alkylene oxide include alkylene oxides such as ethylene oxide, propylene oxide, and butylene oxide. These alkylene oxides can be used alone or in combination of two or more. When two or more types are used, the polyalkylene oxide group (b1) may be random or block. Among these alkylene oxides, ethylene oxide and propylene oxide are preferable, and propylene oxide is more preferable because of higher antifouling properties and good compatibility with other components. Moreover, when the alkylene oxide unit of the said polyalkylene ether group (b1) is made into one repeating unit, the number of repeating units is preferably 1-30 on average, more preferably 2-20, and more preferably 4-15. Are more preferred.

  Examples of the reactive functional group (b2) possessed by the monomer (B1) include a hydroxyl group, an isocyanate group, an epoxy group, a carboxyl group, and a carboxylic acid halide group. As for the monomer (B1) having these reactive functional groups (b2), the reactive functional group (b2) may be used alone or in combination of two or more different reactive functional groups (b2). You can also The polyalkylene ether chain (b1) and the reactive functional group (b2) may be separately contained in the monomer (B1), but the end of the polyalkylene ether chain (b1) is In the case of a reactive functional group such as a hydroxyl group, the polyalkylene ether group (b1) can also serve as the reactive functional group (b2). The radically polymerizable unsaturated group possessed by the monomer (B) is preferably a carbon-carbon unsaturated double bond having radical polymerizability, and more specifically, a vinyl group, a (meth) acryloyl group, a maleimide group. (Meth) acryloyl group is more preferable from the viewpoint of easy polymerization.

  Specific examples of the monomer (B1) include polypropylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, polytetramethylene glycol (meth) acrylate, and poly (ethylene glycol / propylene glycol) mono (meth). Acrylate, polyethylene glycol / polypropylene glycol mono (meth) acrylate, poly (ethylene glycol / tetramethylene glycol) mono (meth) acrylate, polyethylene glycol / polytetramethylene glycol mono (meth) acrylate, poly (propylene glycol / tetramethylene glycol) Mono (meth) acrylate, polypropylene glycol / polytetramethylene glycol mono (meth) acrylate, poly (propylene group) Cole / butylene glycol) mono (meth) acrylate, polypropylene glycol / polybutylene glycol mono (meth) acrylate, poly (ethylene glycol / butylene glycol) mono (meth) acrylate, polyethylene glycol / polybutylene glycol mono (meth) acrylate, poly (Tetraethylene glycol / butylene glycol) mono (meth) acrylate, polytetraethylene glycol / polybutylene glycol mono (meth) acrylate, polybutylene glycol mono (meth) acrylate, poly (ethylene glycol / trimethylene glycol) mono (meth) Acrylate, polyethylene glycol / polytrimethylene glycol mono (meth) acrylate, poly (propylene glycol / trimethyl) Glycol) mono (meth) acrylate, polypropylene glycol / polytrimethylene glycol mono (meth) acrylate, poly (trimethylene glycol / tetramethylene glycol) mono (meth) acrylate, polytrimethylene glycol / polytetramethylene glycol mono (meta) ) Acrylate, poly (butylene glycol / trimethylene glycol) mono (meth) acrylate, polybutylene glycol / polytrimethylene glycol mono (meth) acrylate, and the like. “Poly (ethylene glycol / propylene glycol)” means a random copolymer of ethylene glycol and propylene glycol, and “polyethylene glycol / polypropylene glycol” means a random copolymer of ethylene glycol and propylene glycol. means. The same applies to other items. Among these monomers (B1), the polyalkylene ether chain (b1) can also serve as the reactive functional group (b2), and compatibility with other components is improved. (Meth) acrylate and polyethylene glycol mono (meth) acrylate are preferred.

  In the above production methods 1 to 4, the compound (C) that is a raw material of the fluorine-containing curable resin of the present invention will be described. Examples of the functional group (c) that the compound (C) has include a hydroxyl group, an isocyanate group, an epoxy group, a carboxyl group, and a carboxylic acid halide group. When the reactive functional group (b2) possessed by the monomer (B1) is a hydroxyl group, examples of the functional group (c) include an isocyanate group, a carboxyl group, a carboxylic acid halide group, and an epoxy group. When the group (b2) is an isocyanate group, examples of the functional group (c) include a hydroxyl group. When the reactive functional group (b2) is an epoxy group, the functional group (c) includes a carboxyl group and a hydroxyl group. When the reactive functional group (b2) is a carboxyl group, examples of the functional group (c) include an epoxy group and a hydroxyl group. These may be a combination of a plurality of functional groups. Further, the radically polymerizable unsaturated group of the compound (C) is preferably a carbon-carbon unsaturated double bond having radical polymerizability, and more specifically, a vinyl group, a (meth) acryloyl group, a maleimide group. (Meth) acryloyl group is more preferable from the viewpoint of good curability in the active energy ray-curable resin composition described below.

  Specific examples of the compound (C) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxy Butyl (meth) acrylate, 1,4-cyclohexanedimethanol mono (meth) acrylate, N- (2-hydroxyethyl) (meth) acrylamide, glycerin mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (Meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2- (meth) acryloyloxyethyl-2-hydroxyethyl phthalate, terminal hydroxyl group-containing lactone-modified (meth) acrylate Hydroxyl group-containing unsaturated monomers such as 2- (meth) acryloyloxyethyl isocyanate, 2- (2- (meth) acryloyloxyethoxy) ethyl isocyanate, 1,1-bis ((meth) acryloyloxymethyl) ethyl Isocyanate group-containing unsaturated monomers such as isocyanate; Epoxy group-containing unsaturated monomers such as glycidyl methacrylate and 4-hydroxybutyl acrylate glycidyl ether; (meth) acrylic acid, 2- (meth) acryloyloxyethyl succinic acid, Carboxyl group-containing unsaturated monomers such as 2- (meth) acryloyloxyethyl phthalic acid, maleic acid and itaconic acid; acid anhydrides having an unsaturated double bond such as maleic anhydride and itaconic anhydride . Moreover, 2-hydroxy-3-acryloyloxypropyl methacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate etc. can also be used as what has a some radical polymerizable unsaturated group. These compounds (C) can be used alone or in combination of two or more.

  Among the specific examples of the compound (C), 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, 4-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate are preferable. Hydroxybutyl acrylate, 1,4-cyclohexanedimethanol monoacrylate, N- (2-hydroxyethyl) acrylamide, 2-acryloyloxyethyl isocyanate, 4-hydroxybutyl acrylate glycidyl ether and acrylic acid are preferred.

  The said monomer (B2) used as the raw material of the fluorine-containing curable resin of this invention in the said manufacturing method 2 is demonstrated. The polyalkylene ether chain (b1) possessed by the monomer (B2) may be the same as described for the monomer (B1).

  Specific examples of the monomer (B2) include those listed as specific examples of the monomer (B1). In addition, methoxypolyethylene glycol mono (meth) acrylate, octoxypolyethylene Glycol / polypropylene glycol mono (meth) acrylate, Lauroxy polyethylene glycol mono (meth) acrylate, stearoxy polyethylene glycol mono (meth) acrylate, phenoxy polyethylene glycol mono (meth) acrylate, phenoxy polyethylene glycol / polypropylene glycol mono (meth) acrylate , Nonylphenoxy polypropylene glycol mono (meth) acrylate, Nonylphenoxy poly (ethylene glycol / propylene glycol) mono (meth) acrylate And the like. These monomers (B2) can be used alone or in combination of two or more.

  The said manufacturing method 2-4 WHEREIN: The said monomer (B3) used as the raw material of the fluorine-containing curable resin of this invention is demonstrated. The reactive functional group (b2) included in the monomer (B3) has the same meaning as the reactive functional group (b2) included in the monomer (B1) described above. Moreover, the radically polymerizable unsaturated group that the monomer (B3) has is preferably a carbon-carbon unsaturated double bond having radical polymerizability, more specifically, a vinyl group, a (meth) acryloyl group, Examples thereof include a maleimide group, and a (meth) acryloyl group is more preferable from the viewpoint of easy polymerization.

  Specific examples of the monomer (B3) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4 -Hydroxybutyl (meth) acrylate, 1,4-cyclohexanedimethanol mono (meth) acrylate, N- (2-hydroxyethyl) (meth) acrylamide, glycerin mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene Glycol mono (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2- (meth) acryloyloxyethyl-2-hydroxyethyl phthalate, terminal hydroxyl group-containing lactone-modified (meth) acrylate Hydroxyl group-containing unsaturated monomers such as carbonates; 2- (meth) acryloyloxyethyl isocyanate, 2- (2- (meth) acryloyloxyethoxy) ethyl isocyanate, 1,1-bis ((meth) acryloyloxymethyl) Isocyanate group-containing unsaturated monomers such as ethyl isocyanate; Epoxy group-containing unsaturated monomers such as glycidyl methacrylate and 4-hydroxybutyl acrylate glycidyl ether; (meth) acrylic acid, 2- (meth) acryloyloxyethyl succinic acid Carboxyl group-containing unsaturated monomers such as 2- (meth) acryloyloxyethylphthalic acid, maleic acid and itaconic acid; acid anhydrides having an unsaturated double bond such as maleic anhydride and itaconic anhydride It is done. These monomers (B3) can be used alone or in combination of two or more.

  In the production methods 3 and 4, the compound (A ′) that is a raw material for the fluorine-containing curable resin of the present invention will be described. As the poly (perfluoroalkylene ether) chain of the compound (A ′), the same one as that of the compound (A) described above can be used. Examples of the functional group (a) of the compound (A ′) include a hydroxyl group, an isocyanate group, an epoxy group, a carboxyl group, and a carboxylic acid halide group. When the reactive functional group (b2) of the monomer (B3) used in Production Method 3 or 4 is a hydroxyl group, the functional group (b3) is an isocyanate group, a carboxyl group, a carboxylic acid halide group, or an epoxy. When the reactive functional group (b2) is an isocyanate group, the functional group (b3) includes a hydroxyl group, and when the reactive functional group (b2) is an epoxy group, the functional group Examples of (b3) include a carboxyl group and a hydroxyl group. When the reactive functional group (b2) is a carboxyl group, examples of the functional group (b3) include an epoxy group and a hydroxyl group. These may be a combination of a plurality of functional groups.

  Specific examples of the compound (A ′) include compounds represented by the following structural formulas A′-1 to A′-6, and polyfunctional isocyanate compounds such as hexamethylene diisocyanate and tolylene diisocyanate. And a compound modified with a bifunctional epoxy resin such as a bisphenol-type epoxy resin. In the following structural formulas, “—PFPE—” represents a poly (perfluoroalkylene ether) chain. Among these, the compounds represented by the following structural formulas A′-1 to A′-6 that are not modified are preferable, and in particular, the reactive functional group (b2) of the monomer (B3) is an isocyanate group. The compound represented by the following structural formula A′-1 is preferable from the viewpoint of excellent reactivity with the functional group (b2).

  In the production method 3, the compound (B4) that is a raw material of the fluorinated curable resin of the present invention will be described. As the polyalkylene ether chain (b1) of the compound (B4), the same one as described for the monomer (B1) can be used. Moreover, as a functional group (b3) which the said compound (B4) has, a hydroxyl group, an isocyanate group, an epoxy group, a carboxyl group, a carboxylic acid halide group etc. are mentioned, for example. When the reactive functional group (b2) of the monomer (B3) used in Production Method 3 is a hydroxyl group, the functional group (b3) includes an isocyanate group, a carboxyl group, a carboxylic acid halide group, and an epoxy group. When the reactive functional group (b2) is an isocyanate group, the functional group (b3) includes a hydroxyl group, and when the reactive functional group (b2) is an epoxy group, the functional group (b3 ) Include a carboxyl group and a hydroxyl group. When the reactive functional group (b2) is a carboxyl group, the functional group (b3) includes an epoxy group and a hydroxyl group. These may be a combination of a plurality of functional groups. Furthermore, the radically polymerizable unsaturated group that the compound (B4) has is preferably a carbon-carbon unsaturated double bond having radical polymerizability, and more specifically, a vinyl group, a (meth) acryloyl group, a maleimide group. (Meth) acryloyl group is more preferable from the viewpoint of good curability in the active energy ray-curable resin composition described below.

  Specific examples of the compound (B4) include the same compounds as the specific examples of the monomer (B1). These compounds (B4) can be used alone or in combination of two or more.

  In the production method 4, the compound (B5) that is a raw material of the fluorine-containing curable resin of the present invention will be described. As the polyalkylene ether chain (b1) of the compound (B5), the same one as described for the monomer (B1) can be used. Moreover, as a functional group (b3) which the said compound (B5) has, a hydroxyl group, an isocyanate group, an epoxy group, a carboxyl group, a carboxylic acid halide group etc. are mentioned, for example. When the reactive functional group (b2) of the monomer (B3) used in Production Method 4 is a hydroxyl group, the functional group (b3) includes an isocyanate group, a carboxyl group, a carboxylic acid halide group, and an epoxy group. When the reactive functional group (b2) is an isocyanate group, the functional group (b3) includes a hydroxyl group, and when the reactive functional group (b2) is an epoxy group, the functional group (b3 ) Include a carboxyl group and a hydroxyl group. When the reactive functional group (b2) is a carboxyl group, the functional group (b3) includes an epoxy group and a hydroxyl group. These may be a combination of a plurality of functional groups. Furthermore, the radically polymerizable unsaturated group that the compound (B5) has is preferably a carbon-carbon unsaturated double bond having radical polymerizability, and more specifically, a vinyl group, a (meth) acryloyl group, a maleimide group. (Meth) acryloyl group is more preferable from the viewpoint of good curability in the active energy ray-curable resin composition described below.

  Specific examples of the compound (B5) are the same as those given as specific examples of the monomer (B1). In addition, polypropylene glycol, polyethylene glycol, polytetramethylene glycol, poly (ethylene glycol)・ Propylene glycol), polyethylene glycol / polypropylene glycol, poly (ethylene glycol / tetramethylene glycol), polyethylene glycol / polytetramethylene glycol, poly (propylene glycol / tetramethylene glycol), polypropylene glycol / polytetramethylene glycol, poly (propylene) Glycol / butylene glycol), polypropylene glycol / polybutylene glycol, poly (ethylene glycol / butylene glycol), polyethylene Glycol / polybutylene glycol, poly (tetraethylene glycol / butylene glycol), polytetraethylene glycol / polybutylene glycol, polybutylene glycol, poly (ethylene glycol / trimethylene glycol), polyethylene glycol / polytrimethylene glycol, poly ( Propylene glycol / trimethylene glycol), polypropylene glycol / polytrimethylene glycol, poly (trimethylene glycol / tetramethylene glycol), polytrimethylene glycol / polytetramethylene glycol, poly (butylene glycol / trimethylene glycol), polybutylene glycol・ Polyalkylene glycol such as polytrimethylene glycol where both ends are hydroxyl groups; methoxypolyethylene Pieces such as lenglycol, octoxypolyethyleneglycol / polypropyleneglycol, lauroxypolyethyleneglycol, stearoxypolyethyleneglycol, phenoxypolyethyleneglycol, phenoxypolyethyleneglycol / polypropyleneglycol, nonylphenoxypolypropyleneglycol, nonylphenoxypoly (ethyleneglycol / propyleneglycol), etc. Examples include polyalkylene glycol having a hydroxyl group only at the terminal. These compounds (B5) can be used alone or in combination of two or more.

  Moreover, in the said manufacturing methods 1-4, when manufacturing the said polymer (P1) or (P2) which is an intermediate body of the fluorine-containing curable resin of this invention, the said compound (A), monomer (B1) In addition to the monomer (B2) and the monomer (B3), other radical polymerizable unsaturated monomers that can be copolymerized with these may be used. Examples of such other radical polymerizable unsaturated monomers include methyl (meth) acrylate, ethyl (meth) acrylate, (meth) acrylate-n-propyl, (meth) acrylate-n-butyl, (Meth) acrylic acid isobutyl, (meth) acrylic acid-n-pentyl, (meth) acrylic acid-n-hexyl, (meth) acrylic acid-n-heptyl, (meth) acrylic acid-n-octyl, (meth) (Meth) acrylates such as 2-ethylhexyl acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate Aromatic vinyls such as styrene, α-methylstyrene, p-methylstyrene, p-methoxystyrene; maleimide, methylmer Imides, ethylmaleimide, propyl maleimide, butyl maleimide, hexyl maleimide, octyl maleimide, dodecyl maleimide, stearyl maleimide, phenyl maleimide, and the like maleimides such as cyclohexyl maleimide.

  Next, a more specific method for producing the fluorine-containing curable resin of the present invention will be described using the raw materials listed above.

  In the production methods 1 to 4, the method for producing the polymer (P1), (P2) or (P3), which is an intermediate of the fluorine-containing curable resin of the present invention, (A) and the monomer (B1), and if necessary, other radical polymerizable unsaturated monomers, in the case of production method 2, the compound (A), the monomer (B2) and In the case of production method 3 or 4, the monomer (B3) and, if necessary, other radicals, other radical polymerizable unsaturated monomers. Examples thereof include a method of polymerizing a polymerizable unsaturated monomer in an organic solvent using a radical polymerization initiator. As the organic solvent used here, ketones, esters, amides, sulfoxides, ethers, hydrocarbons are preferable. Specifically, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, butyl acetate, Examples include propylene glycol monomethyl ether acetate, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, toluene, xylene and the like. These are appropriately selected in consideration of boiling point, compatibility, and polymerizability. Examples of the radical polymerization initiator include peroxides such as benzoyl peroxide and azo compounds such as azobisisobutyronitrile. Furthermore, chain transfer agents such as lauryl mercaptan, 2-mercaptoethanol, thioglycerol, ethylthioglycolic acid, octylthioglycolic acid and the like can be used as necessary.

  The molecular weight of the resulting polymer (P1), (P2) or (P3) can suppress insolubilization of the polymer produced by the crosslinking reaction that occurs during the polymerization into the solvent, and is 1 of the radically polymerizable resin that is finally obtained. The polymer (P1), (P2) or (P3) has a number average molecular weight (Mn) of 800 to 3,000, particularly 1,000 to 2,500, in that the number of polymerizable unsaturated groups in the molecule increases. The weight average molecular weight (Mw) is preferably in the range of 1,500 to 40,000, particularly 2,000 to 30,000.

  Here, the number average molecular weight (Mn) and the weight average molecular weight (Mw) are values converted to polystyrene based on gel permeation chromatography (hereinafter abbreviated as “GPC”) measurement. The measurement conditions for GPC are as follows.

[GPC measurement conditions]
Measuring device: “HLC-8220 GPC” manufactured by Tosoh Corporation
Column: Guard column “HHR-H” manufactured by Tosoh Corporation (6.0 mm ID × 4 cm)
+ "TSK-GEL GMHHR-N" (7.8 mm ID x 30 cm) manufactured by Tosoh Corporation
+ "TSK-GEL GMHHR-N" (7.8 mm ID x 30 cm) manufactured by Tosoh Corporation
+ "TSK-GEL GMHHR-N" (7.8 mm ID x 30 cm) manufactured by Tosoh Corporation
+ "TSK-GEL GMHHR-N" (7.8 mm ID x 30 cm) manufactured by Tosoh Corporation
Detector: ELSD ("ELSD2000" manufactured by Oltec)
Data processing: “GPC-8020 Model II data analysis version 4.30” manufactured by Tosoh Corporation
Measurement conditions: Column temperature 40 ° C
Developing solvent Tetrahydrofuran (THF)
Flow rate 1.0 ml / min Sample: A 1.0% by mass tetrahydrofuran solution filtered in terms of resin solids through a microfilter (100 μl).
Standard sample: The following monodisperse polystyrene having a known molecular weight was used in accordance with the measurement manual of “GPC-8020 Model II Data Analysis Version 4.30”.

(Monodispersed polystyrene)
“A-500” manufactured by Tosoh Corporation
"A-1000" manufactured by Tosoh Corporation
"A-2500" manufactured by Tosoh Corporation
"A-5000" manufactured by Tosoh Corporation
“F-1” manufactured by Tosoh Corporation
"F-2" manufactured by Tosoh Corporation
“F-4” manufactured by Tosoh Corporation
“F-10” manufactured by Tosoh Corporation
“F-20” manufactured by Tosoh Corporation
“F-40” manufactured by Tosoh Corporation
“F-80” manufactured by Tosoh Corporation
“F-128” manufactured by Tosoh Corporation
“F-288” manufactured by Tosoh Corporation
“F-550” manufactured by Tosoh Corporation

  In the production method 1 or 2, the polymer (P1) or (P2) obtained as described above is reacted with the functional group (c) having reactivity with the functional group (b2) and the radically polymerizable unsaturated group. The fluorine-containing curable resin of the present invention is obtained by reacting the compound (C) having a group. In Production Method 3, the compound (A ′) and the compound (B4) are reacted with the polymer (P3) obtained as described above, and the compound (C) is further reacted as necessary. By doing so, the fluorine-containing curable resin of the present invention is obtained. Furthermore, in the production method 4, the polymer (P3) obtained as described above is reacted with the compound (A ′), the compound (B5), and the compound (C) to thereby include the present invention. A fluorine curable resin is obtained.

  The polymer (P1), (P2) or (P3) is reacted with the compound (C), the compound (A ′), the compound (B4), or the compound (B5) by the compound (C). The radically polymerizable unsaturated group possessed by the above-mentioned groups may be carried out under conditions that do not polymerize. This reaction is preferably carried out in the presence of a catalyst or a polymerization inhibitor, and if necessary in the presence of an organic solvent.

  For example, when the functional group (b2) is a hydroxyl group and the functional group (c), the functional group (a), and the functional group (b3) are isocyanate groups, or the functional group (b2) is When it is an isocyanate group and the functional group (c), the functional group (a), and the functional group (b3) are hydroxyl groups, p-methoxyphenol, hydroquinone, 2,6-di- t-butyl-4-methylphenol or the like is used, dibutyltin dilaurate, dibutyltin diacetate, tin octylate, zinc octylate or the like is used as the urethanization reaction catalyst, and the reaction temperature is 40 to 120 ° C., particularly 60 to 90. A method of reacting at 0 ° C. is preferred. When the functional group (b2) is an epoxy group and the functional group (c), the functional group (a), and the functional group (b3) are carboxyl groups, or the functional group (b2) Is a carboxyl group and the functional group (c), the functional group (a), and the functional group (b3) are epoxy groups, p-methoxyphenol, hydroquinone, 2,6- Di-t-butyl-4-methylphenol and the like, tertiary amines such as triethylamine as the esterification reaction catalyst, quaternary ammoniums such as tetramethylammonium chloride, and tertiary phosphine such as triphenylphosphine And quaternary phosphoniums such as tetrabutylphosphonium chloride and the like, and the reaction is preferably performed at a reaction temperature of 80 to 130 ° C, particularly 100 to 120 ° C.

  The organic solvent used in the above reaction is preferably ketones, esters, amides, sulfoxides, ethers, hydrocarbons, specifically, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, butyl acetate, Examples include propylene glycol monomethyl ether acetate, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, toluene, xylene and the like. These may be appropriately selected in consideration of the boiling point and compatibility.

  Since the fluorine-containing curable resin of the present invention obtained as described above can prevent gelation during production and has excellent antifouling properties, its number average molecular weight (Mn) is 1,000 to 5,000. The range is preferable, and the range of 1,500 to 4,000 is more preferable. Moreover, it is preferable that a weight average molecular weight (Mw) is the range of 3,000-100,000, and it is more preferable that it is the range of 4,000-40,000. These number average molecular weight (Mn) and weight average molecular weight (Mw) can be determined by the above GPC measurement.

  In addition, the fluorine content in the fluorine-containing curable resin of the present invention is preferably in the range of 2 to 40% by mass because both antifouling properties and compatibility with other components can be achieved. The range of 30% by mass is more preferable, and the range of 10 to 20% by mass is more preferable. The fluorine content in the fluorine-containing radical polymerizable copolymer of the present invention is calculated from the mass ratio of fluorine atoms with respect to the total amount of raw materials used.

  The fluorine-containing curable resin of the present invention can be used as a main component of the active energy ray-curable coating composition itself, but has an extremely excellent surface modification performance. By using it as a fluorosurfactant added to the composition, excellent antifouling properties can be imparted to the cured coating film.

  The active energy ray curable coating composition of the present invention is a blend of the fluorine-containing curable resin of the present invention, and the main component thereof is an active energy ray curable resin (D) or active energy ray curable. Containing a reactive monomer (E). In the active energy ray curable coating composition of the present invention, the active energy ray curable resin (D) and the active energy ray curable monomer (E) may be used alone or in combination. It doesn't matter. The fluorine-containing curable resin of the present invention is preferably used as a fluorine-based surfactant in the active energy ray-curable coating composition.

  The active energy ray-curable resin (D) is a urethane (meth) acrylate resin, unsaturated polyester resin, epoxy (meth) acrylate resin, polyester (meth) acrylate resin, acrylic (meth) acrylate resin, maleimide group-containing resin, etc. In the present invention, a urethane (meth) acrylate resin is particularly preferable from the viewpoint of transparency and low shrinkage.

  The urethane (meth) acrylate resin used here is a resin having a urethane bond and a (meth) acryloyl group obtained by reacting an aliphatic polyisocyanate compound or an aromatic polyisocyanate compound with a hydroxy group-containing (meth) acrylate compound. Is mentioned.

  Examples of the aliphatic polyisocyanate compound include tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate (hereinafter abbreviated as HDI), heptamethylene diisocyanate, octamethylene diisocyanate, decamethylene diisocyanate, 2-methyl-1, 5-pentane diisocyanate, 3-methyl-1,5-pentane diisocyanate, dodecamethylene diisocyanate, 2-methylpentamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, isophorone Diisocyanate, norbornane diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated tolylene diisocyanate And hydrogenated xylylene diisocyanate, hydrogenated tetramethyl xylylene diisocyanate, cyclohexyl diisocyanate and the like, and examples of the aromatic polyisocyanate compound include tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, xylylene diisocyanate, 1 , 5-naphthalene diisocyanate, tolidine diisocyanate, p-phenylene diisocyanate and the like.

  On the other hand, examples of the hydroxy group-containing acrylate compound include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 1, Monovalent dihydric alcohols such as 5-pentanediol mono (meth) acrylate, 1,6-hexanediol mono (meth) acrylate, neopentyl glycol mono (meth) acrylate, and hydroxypivalate neopentyl glycol mono (meth) acrylate ( (Meth) acrylate; trimethylolpropane di (meth) acrylate, ethoxylated trimethylolpropane (meth) acrylate, propoxylated trimethylolpropane di (meth) acrylate, glycerin di (meth) Mono- or di (meth) acrylates of trivalent alcohols such as acrylate and bis (2- (meth) acryloyloxyethyl) hydroxyethyl isocyanurate, or hydroxyl groups obtained by modifying some of these alcoholic hydroxyl groups with ε-caprolactone Containing mono- and di (meth) acrylates; monofunctional hydroxyl groups such as pentaerythritol tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and more than trifunctional (meth) acryloyl groups Or a hydroxyl group-containing polyfunctional (meth) acrylate further modified with ε-caprolactone; dipropylene glycol mono (meth) acrylate, diethylene glycol mono (meth) acrylate, polypropylene (Meth) acrylate compounds having an oxyalkylene chain such as polyethylene glycol mono (meth) acrylate and polyethylene glycol mono (meth) acrylate; polyethylene glycol-polypropylene glycol mono (meth) acrylate, polyoxybutylene-polyoxypropylene mono (meth) (Meth) acrylate compounds having a block structure oxyalkylene chain such as acrylate; random structures such as poly (ethylene glycol-tetramethylene glycol) mono (meth) acrylate and poly (propylene glycol-tetramethylene glycol) mono (meth) acrylate And (meth) acrylate compounds having an oxyalkylene chain.

  The reaction of the above-mentioned aliphatic polyisocyanate compound or aromatic polyisocyanate compound and the hydroxy group-containing acrylate compound can be carried out by a conventional method in the presence of a urethanization catalyst. Specific examples of urethanization catalysts that can be used here include amines such as pyridine, pyrrole, triethylamine, diethylamine, and dibutylamine, phosphines such as triphenylphosphine and triethylphosphine, dibutyltin dilaurate, octyltin trilaurate, and octyl. Examples thereof include organotin compounds such as tin diacetate, dibutyltin diacetate, and tin octylate, and organometallic compounds such as zinc octylate.

  Among these urethane acrylate resins, those obtained by reacting an aliphatic polyisocyanate compound with a hydroxy group-containing (meth) acrylate compound are excellent in transparency of the cured coating film and have good sensitivity to active energy rays. It is preferable from the viewpoint of excellent curability.

  Next, the unsaturated polyester resin is a curable resin obtained by polycondensation of α, β-unsaturated dibasic acid or acid anhydride thereof, aromatic saturated dibasic acid or acid anhydride thereof, and glycols. The α, β-unsaturated dibasic acid or its acid anhydride includes maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, chloromaleic acid, and esters thereof. As aromatic saturated dibasic acid or acid anhydride thereof, phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, nitrophthalic acid, tetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, halogenated phthalic anhydride and these Examples include esters. Examples of the aliphatic or alicyclic saturated dibasic acid include oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, glutaric acid, hexahydrophthalic anhydride, and esters thereof. As glycols, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, 2-methylpropane-1,3-diol, neopentyl glycol, triethylene glycol, Examples include tetraethylene glycol, 1,5-pentanediol, 1,6-hexanediol, bisphenol A, hydrogenated bisphenol A, ethylene glycol carbonate, 2,2-di- (4-hydroxypropoxydiphenyl) propane, and others. In addition, oxides such as ethylene oxide and propylene oxide can be used in the same manner.

  Next, as an epoxy vinyl ester resin, (meth) acrylic acid is reacted with an epoxy group of an epoxy resin such as a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a phenol novolac type epoxy resin, or a cresol novolak type epoxy resin. What is obtained is mentioned.

  Further, as the maleimide group-containing resin, a bifunctional maleimide urethane compound obtained by urethanizing N-hydroxyethylmaleimide and isophorone diisocyanate, a bifunctional maleimide ester compound obtained by esterifying maleimide acetic acid and polytetramethylene glycol, Examples thereof include a tetrafunctional maleimide ester compound obtained by esterification of maleimidocaproic acid and a tetraethylene oxide adduct of pentaerythritol, a polyfunctional maleimide ester compound obtained by esterification of maleimide acetic acid and a polyhydric alcohol compound, and the like. These active energy ray-curable resins (F) can be used alone or in combination of two or more.

  Examples of the active energy ray-curable monomer (E) include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, and a number average molecular weight in the range of 150 to 1,000. Polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di having a number average molecular weight in the range of 150 to 1000 (Meth) acrylate, neopentyl glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol (Meth) acrylate, hydroxypivalate ester neopentyl glycol di (meth) acrylate, bisphenol A di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol Hexa (meth) acrylate, pentaerythritol tetra (meth) acrylate, trimethylolpropane di (meth) acrylate, dipentaerythritol penta (meth) acrylate, dicyclopentenyl (meth) acrylate, methyl (meth) acrylate, Propyl (meth) acrylate, butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, decyl (meta Aliphatic alkyl (meth) acrylates such as acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, glycerol (meth) acrylate, 2-hydroxyethyl (meth) acrylate , 3-chloro-2-hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate, allyl (meth) acrylate, 2-butoxyethyl (meth) acrylate, 2- (diethylamino) ethyl (meth) acrylate, 2- (dimethyl Amino) ethyl (meth) acrylate, γ- (meth) acryloxypropyltrimethoxysilane, 2-methoxyethyl (meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxydi Lopylene glycol (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, nonylphenoxypolypropylene glycol (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydipropylene glycolicol (meth) acrylate, phenoxypolypropylene glycol (meth) acrylate, Polybutadiene (meth) acrylate, polyethylene glycol-polypropylene glycol (meth) acrylate, polyethylene glycol-polybutylene glycol (meth) acrylate, polystyrylethyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopenta Nyl (meth) acrylate, dicyclopentenyl (meth) acryl , Isobornyl (meth) acrylate, methoxylated cyclodecatriene (meth) acrylate, phenyl (meth) acrylate; maleimide, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-butylmaleimide, N-hexyl Maleimide, N-octylmaleimide, N-dodecylmaleimide, N-stearylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide, 2-maleimidoethyl-ethylcarbonate, 2-maleimidoethyl-propylcarbonate, N-ethyl- (2- Maleimidoethyl) carbamate, N, N-hexamethylene bismaleimide, polypropylene glycol-bis (3-maleimidopropyl) ether, bis (2-maleimidoethyl) carbonate, 1,4-di And maleimides such as maleimide cyclohexane.

  Among these, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, pentaerythritol tetra ( A trifunctional or higher polyfunctional (meth) acrylate such as (meth) acrylate is preferred. These active energy ray-curable monomers (E) can be used alone or in combination of two or more.

  In the active energy ray-curable coating composition of the present invention, when the fluorine-containing curable resin of the present invention is used as a fluorosurfactant, the amount used thereof is the active energy ray-curable resin (D) and the active energy. It is preferably in the range of 0.01 to 10 parts by mass, more preferably in the range of 0.1 to 5% by mass, with respect to 100 parts by mass in total of the linear curable monomer (E). If the amount of the fluorine-containing curable resin of the present invention is within this range, leveling properties, water / oil repellency and antifouling properties can be made sufficient, and the hardness and transparency of the coating composition after curing can be improved. The property can also be sufficient.

  The fluorine-containing curable resin or active energy ray-curable coating composition of the present invention can be formed into a cured coating film by irradiating active energy rays after being applied to a substrate. The active energy rays refer to ionizing radiation such as ultraviolet rays, electron beams, α rays, β rays, and γ rays. When a cured coating film is formed by irradiating ultraviolet rays as active energy rays, a photopolymerization initiator (F) is added to the fluorine-containing curable resin or active energy ray curable composition to improve curability. It is preferable. Further, if necessary, a photosensitizer can be further added to improve curability. On the other hand, when ionizing radiation such as electron beam, α-ray, β-ray, and γ-ray is used, it cures quickly without using a photopolymerization initiator or photosensitizer. F) or a photosensitizer need not be added.

  Examples of the photopolymerization initiator (F) include intramolecular cleavage type photopolymerization initiators and hydrogen abstraction type photopolymerization initiators. Examples of the intramolecular cleavage type photopolymerization initiator include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy. 2-methylpropan-1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl-phenylketone, 2-methyl-2-morpholino (4-thio) Acetophenone-based compounds such as methylphenyl) propan-1-one and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone; benzoins such as benzoin, benzoin methyl ether and benzoin isopropyl ether; 4,6-trimethylbenzoindiphenylphos In'okishido, bis (2,4,6-trimethylbenzoyl) - acyl phosphine oxide-based compounds such as triphenylphosphine oxide; benzyl, and methyl phenylglyoxylate ester.

  On the other hand, examples of the hydrogen abstraction type photopolymerization initiator include benzophenone, methyl 4-phenylbenzophenone, o-benzoylbenzoate, 4,4′-dichlorobenzophenone, hydroxybenzophenone, 4-benzoyl-4′-methyl-diphenyl sulfide. Benzophenone compounds such as acrylated benzophenone, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, 3,3′-dimethyl-4-methoxybenzophenone; 2-isopropylthioxanthone, 2,4 A thioxanthone compound such as dimethylthioxanthone, 2,4-diethylthioxanthone, and 2,4-dichlorothioxanthone; an aminobenzophenone compound such as Michler's ketone and 4,4′-diethylaminobenzophenone; 2-chloro acridone, 2-ethyl anthraquinone, 9,10-phenanthrenequinone, camphorquinone, and the like.

  Among the photopolymerization initiators (F), the compatibility with the active energy ray curable resin (D) and the active energy ray curable monomer (E) in the active energy ray curable coating composition is excellent. From the viewpoint, 1-hydroxycyclohexyl phenyl ketone and benzophenone are preferable, and 1-hydroxycyclohexyl phenyl ketone is particularly preferable. These photopolymerization initiators (F) can be used alone or in combination of two or more.

  Examples of the photosensitizer include amines such as aliphatic amines and aromatic amines, ureas such as o-tolylthiourea, sodium diethyldithiophosphate, s-benzylisothiuronium-p-toluenesulfonate, and the like. And sulfur compounds.

  These photopolymerization initiators and photosensitizers are preferably used in an amount of 0.01 to 20 parts by weight, preferably 0.1 to 15 parts by weight, based on 100 parts by weight of the nonvolatile component in the active energy ray-curable composition. % Is more preferable, and 0.3 to 7 parts by mass is more preferable.

  Furthermore, the active energy ray-curable coating composition of the present invention can be used to adjust the viscosity and refractive index, or to adjust the color tone of the coating film within the range that does not impair the effects of the present invention, depending on the purpose of use, characteristics, etc. Various compounding materials for the purpose of adjusting other paint properties and coating film properties, for example, various organic solvents, acrylic resins, phenol resins, polyester resins, polystyrene resins, urethane resins, urea resins, melamine resins, alkyd resins, epoxy resins Various resins such as polyamide resin, polycarbonate resin, petroleum resin, fluororesin, PTFE (polytetrafluoroethylene), polyethylene, polypropylene, carbon, titanium oxide, alumina, copper, silica fine particles, polymerized Initiator, polymerization inhibitor, antistatic agent, antifoaming agent, viscosity modifier, light resistance stabilizer, weather resistance stabilizer, Thermal stabilizers, antioxidants, rust inhibitors, slip agents, waxes, gloss modifiers, mold release agents, compatibilizers, conductivity modifiers, pigments, dyes, dispersants, dispersion stabilizers, silicones, hydrocarbons A surfactant or the like can be used in combination.

  Among the above ingredients, the organic solvent is useful for appropriately adjusting the solution viscosity of the active energy ray-curable coating composition of the present invention, and in particular, for thin film coating, the film thickness should be adjusted. Becomes easy. Examples of the organic solvent that can be used here include aromatic hydrocarbons such as toluene and xylene; alcohols such as methanol, ethanol, isopropanol, and t-butanol; esters such as ethyl acetate and propylene glycol monomethyl ether acetate; Examples thereof include ketones such as methyl isobutyl ketone and cyclohexanone. These solvents can be used alone or in combination of two or more.

  Here, the amount of the organic solvent used varies depending on the intended use and the target film thickness and viscosity, but is preferably in the range of 0.5 to 4 times the mass of the total mass of the curing component.

  As described above, the active energy ray for curing the active energy ray-curable coating composition of the present invention is ionizing radiation such as ultraviolet rays, electron rays, α rays, β rays, and γ rays, but specific energy. Examples of the light source or curing device include germicidal lamps, fluorescent lamps for ultraviolet rays, carbon arc, xenon lamps, high pressure mercury lamps for copying, medium or high pressure mercury lamps, ultrahigh pressure mercury lamps, electrodeless lamps, metal halide lamps, natural light, etc. Or an electron beam by a scanning type or curtain type electron beam accelerator.

  Among these, ultraviolet rays are particularly preferable, and ultraviolet rays are preferably irradiated in an inert gas atmosphere such as nitrogen gas in order to avoid curing inhibition due to oxygen or the like. Further, if necessary, heat may be used as an energy source and heat treatment may be performed after curing with ultraviolet rays.

  The application method of the active energy ray-curable coating composition of the present invention varies depending on the application. For example, gravure coater, roll coater, comma coater, knife coater, air knife coater, curtain coater, kiss coater, shower coater, wheeler coater, spin Examples thereof include a coating method using a coater, dipping, screen printing, spray, applicator, bar coater, etc., or a molding method using various molds.

  The cured coating film of the fluorine-containing curable resin of the present invention has excellent antifouling properties (ink repellency, fingerprint resistance, etc.), scratch resistance, etc. It is possible to impart antifouling property, scratch resistance, etc. The fluorine-containing curable resin of the present invention can also impart leveling properties to the coating material by adding it as a fluorosurfactant to the coating material. Therefore, the active energy ray-curable coating composition of the present invention The thing has a high leveling property.

  Articles that can be imparted with antifouling properties (ink repellency, fingerprint resistance, etc.) using the fluorine-containing curable resin or the active energy ray-curable coating composition of the present invention include liquid crystal displays (LCD) such as TAC films. Protective film for polarizing plate; various display screens such as plasma display (PDP) and organic EL display; touch panel; mobile phone casing or mobile phone screen; optical recording medium such as CD, DVD, Blu-ray disc; insert mold (IMD, Transfer film for IMF); Rubber roller for OA equipment such as copiers and printers; Glass surface of the reading part of OA equipment such as copiers and scanners; Optical lenses such as cameras, video cameras and glasses; Windshields for watches such as watches , Glass surface; windows for various vehicles such as automobiles and railway vehicles; various building materials such as decorative panels; Glazing; furniture such woodworking materials, artificial-synthetic leather, home appliances of the housing or the like of various plastic molded products, such as FRP bathtubs and the like. By applying the fluorine-containing curable resin or active energy ray-curable coating composition of the present invention to the surface of these articles and irradiating active energy rays such as ultraviolet rays to form a cured coating film, the surface of the article is antifouled. Sex can be imparted. Further, the fluorine-containing curable resin of the present invention can be added to various paints suitable for each article, applied, and dried to impart antifouling properties to the article surface.

  Further, as a coating material that can improve the leveling property by adding the fluorine-containing curable resin of the present invention and impart antifouling properties (ink repellency, fingerprint resistance, etc.) to the coating film, an LCD such as a TAC film can be used. Hard coating material for polarizing film, anti-glare (AG: anti-glare) coating material or anti-reflection (LR) coating material; hard coating material for various display screens such as plasma display and organic EL display (PDP); Coating material: Color resist, printing ink, inkjet ink or paint for forming each pixel of RGB used for a color filter for liquid crystal display (hereinafter referred to as “CF”); Black resist for black matrix of CF, Printing ink, inkjet ink or paint; plasma display (PDP) Resin composition for pixel partition walls of organic EL displays, etc .; paint or hard coat material for mobile phone casings; hard coat material for mobile phone screens; hard coat material for optical recording media such as CD, DVD, Blu-ray disc; insert mold Hard coating material for transfer film for (IMD, IMF); Coating material for rubber roller for OA equipment such as copying machines and printers; Coating material for glass for reading parts of OA equipment such as copying machines and scanners; Cameras, video cameras, Coating materials for optical lenses such as glasses; windshields for watches such as watches; coating materials for glasses; coating materials for windows of various vehicles such as automobiles and railway vehicles; printing inks or paints for various building materials such as decorative panels; Coating materials for glass; wood coatings for furniture, etc .; coating materials for artificial and synthetic leather; various plastic moldings such as housings for home appliances Use paint or coating material; such as FRP tub paint or coating material and the like.

  Further, as an article that can be provided with scratch resistance (scratch resistance) and antifouling property using the fluorine-containing curable resin or active energy ray-curable coating composition of the present invention, a prism sheet that is a backlight member of an LCD Or a diffusion sheet etc. are mentioned. Further, by adding the fluorine-containing curable resin of the present invention to the prism sheet or the diffusion sheet coating material, the leveling property of the coating material is improved and the coating film of the coating material is scratch resistant (scratch resistance). And antifouling property can be provided.

  Further, since the cured coating film of the fluorinated curable resin of the present invention has a low refractive index, the coating for the low refractive index layer in the antireflection layer for preventing the reflection of a fluorescent lamp or the like on the surface of various displays such as LCDs. It can also be used as a material. Further, by adding the fluorine-containing curable resin of the present invention to the coating material for the antireflection layer, particularly the coating material for the low refractive index layer in the antireflection layer, the coating material can be applied while maintaining the low refractive index of the coating film. Antifouling properties can also be imparted to the membrane surface.

  Furthermore, as other applications in which the fluorine-containing curable resin or active energy ray-curable coating composition of the present invention can be used, optical fiber cladding materials, waveguides, liquid crystal panel sealing materials, various optical sealing materials, Examples include optical adhesives.

  In particular, when the active energy ray-curable coating composition of the present invention is used as an antiglare coating material among coating materials for protective films for polarizing plates for LCDs, among the above-mentioned compositions, silica fine particles, acrylic resin fine particles, polystyrene Anti-glare properties are obtained by blending inorganic or organic fine particles such as resin fine particles at a ratio of 0.1 to 0.5 times the total mass of the curing component in the active energy ray-curable coating composition of the present invention. It is preferable because it is excellent.

  In addition, when the fluorine-containing curable resin or the active energy ray-curable coating composition of the present invention is used for an antiglare coating material for a protective film of a polarizing plate for LCD, a mold having an uneven surface shape before the coating material is cured. After the contact, the active energy ray is irradiated from the side opposite to the mold and cured, and the surface of the coating layer is embossed to apply an antiglare property.

Hereinafter, the present invention will be described in more detail with reference to specific examples. In addition, the measurement conditions of IR spectrum of the obtained fluorine-containing curable resin, < ¹³ > C-NMR spectrum, and GPC are as follows.

[IR spectrum measurement conditions]
Apparatus: “IR Prestige-21” manufactured by Shimadzu Corporation
The resins obtained in the examples were measured by the KBr method.

[ ^13C -NMR spectrum measurement conditions]
Apparatus: “AL-400” manufactured by JEOL Ltd.
Solvent: acetone-d ₆

[GPC measurement conditions]
Measuring device: “HLC-8220 GPC” manufactured by Tosoh Corporation
Column: Guard column “HHR-H” manufactured by Tosoh Corporation (6.0 mm ID × 4 cm)
+ "TSK-GEL GMHHR-N" (7.8 mm ID x 30 cm) manufactured by Tosoh Corporation
+ "TSK-GEL GMHHR-N" (7.8 mm ID x 30 cm) manufactured by Tosoh Corporation
+ "TSK-GEL GMHHR-N" (7.8 mm ID x 30 cm) manufactured by Tosoh Corporation
+ "TSK-GEL GMHHR-N" (7.8 mm ID x 30 cm) manufactured by Tosoh Corporation
Detector: ELSD ("ELSD2000" manufactured by Oltec)
Data processing: “GPC-8020 Model II data analysis version 4.30” manufactured by Tosoh Corporation
Measurement conditions: Column temperature 40 ° C
Developing solvent Tetrahydrofuran (THF)
Flow rate 1.0 ml / min Sample: A 1.0% by mass tetrahydrofuran solution filtered in terms of resin solids through a microfilter (100 μl).
Standard sample: The following monodisperse polystyrene having a known molecular weight was used in accordance with the measurement manual of “GPC-8020 Model II Data Analysis Version 4.30”.

(Monodispersed polystyrene)
“A-500” manufactured by Tosoh Corporation
"A-1000" manufactured by Tosoh Corporation
"A-2500" manufactured by Tosoh Corporation
"A-5000" manufactured by Tosoh Corporation
“F-1” manufactured by Tosoh Corporation
"F-2" manufactured by Tosoh Corporation
“F-4” manufactured by Tosoh Corporation
“F-10” manufactured by Tosoh Corporation
“F-20” manufactured by Tosoh Corporation
“F-40” manufactured by Tosoh Corporation
“F-80” manufactured by Tosoh Corporation
“F-128” manufactured by Tosoh Corporation
“F-288” manufactured by Tosoh Corporation
“F-550” manufactured by Tosoh Corporation

(Synthesis Example 1)
A glass flask equipped with a stirrer, a thermometer, a condenser, and a dropping device, 20 parts by mass of a perfluoropolyether compound having a hydroxyl group at both ends represented by the following formula (a2-1-1), and diisopropyl ether as a solvent 20 parts by mass, p-methoxyphenol 0.02 parts by mass as a polymerization inhibitor and 3.1 parts by mass of triethylamine as a neutralizing agent were added, stirring was started under an air stream, and acrylic was maintained while maintaining the inside of the flask at 10 ° C. 2.7 parts by mass of acid chloride was added dropwise over 1 hour. After completion of dropping, the mixture is stirred at 10 ° C. for 1 hour, heated to 30 ° C. for 1 hour, then heated to 50 ° C. and stirred for 10 hours, and acrylic acid is measured by gas chromatography. The disappearance of chloride was confirmed. Next, after adding 40 parts by mass of diisopropyl ether as a solvent, 80 parts by mass of ion-exchanged water was mixed and stirred, and then left to stand to separate and remove the aqueous layer, and washing was repeated 3 times. Subsequently, 0.02 parts by mass of p-methoxyphenol was added as a polymerization inhibitor, 8 parts by mass of magnesium sulfate was added as a dehydrating agent, and the mixture was allowed to stand for 1 day for complete dehydration, and then the dehydrating agent was filtered off. .

（式中、Ｘはパーフルオロメチレン基及びパーフルオロエチレン基であり、１分子あたり、パーフルオロメチレン基が平均７個、パーフルオロエチレン基が平均８個存在するものであり、フッ素原子の数が平均４６である。また、ＧＰＣによる数平均分子量は１，５００である。）

(In the formula, X is a perfluoromethylene group and a perfluoroethylene group, and an average of 7 perfluoromethylene groups and an average of 8 perfluoroethylene groups are present per molecule, and the number of fluorine atoms is (The average is 46. The number average molecular weight by GPC is 1,500.)

  Subsequently, the solvent was distilled off under reduced pressure to obtain a compound having a poly (perfluoroalkylene ether) chain represented by the following formula (A-1-1).

（式中、Ｘはパーフルオロメチレン基及びパーフルオロエチレン基であり、１分子あたり、パーフルオロメチレン基が平均７個、パーフルオロエチレン基が平均８個存在するものであり、フッ素原子の数が平均４６である。）

(In the formula, X is a perfluoromethylene group and a perfluoroethylene group, and an average of 7 perfluoromethylene groups and an average of 8 perfluoroethylene groups are present per molecule, and the number of fluorine atoms is (The average is 46.)

(Synthesis Example 2)
In a glass flask equipped with a stirrer, a thermometer, a condenser, and a dropping device, 20 parts by mass of a perfluoropolyether compound having a hydroxyl group at both ends represented by the above formula (a2-1-1), and diisopropyl ether as a solvent 10 parts by mass, p-methoxyphenol 0.006 parts by mass as a polymerization inhibitor and 3.3 parts by mass of triethylamine as a neutralizing agent were added, stirring was started under an air stream, and methacrylic acid was maintained at 10 ° C. 3.1 parts by mass of acid chloride was added dropwise over 2 hours. After completion of the dropwise addition, the mixture was stirred at 10 ° C. for 1 hour, heated to 30 ° C. for 1 hour, then heated to 50 ° C. and stirred for 10 hours, and methacrylic acid was measured by gas chromatography. The disappearance of chloride was confirmed. Next, after adding 70 parts by mass of diisopropyl ether as a solvent, 80 parts by mass of ion-exchanged water was mixed, stirred, and allowed to stand, and washing by a method of separating and removing the aqueous layer was repeated three times. Subsequently, 0.02 parts by mass of p-methoxyphenol was added as a polymerization inhibitor, 8 parts by mass of magnesium sulfate was added as a dehydrating agent, and the mixture was allowed to stand for 1 day for complete dehydration, and then the dehydrating agent was filtered off. .

  Next, the solvent was distilled off under reduced pressure to obtain a compound having a poly (perfluoroalkylene ether) chain represented by the following formula (A-2-1).

（式中、Ｘはパーフルオロメチレン基及びパーフルオロエチレン基であり、１分子あたり、パーフルオロメチレン基が平均７個、パーフルオロエチレン基が平均８個存在するものであり、フッ素原子の数が平均４６である。）

(In the formula, X is a perfluoromethylene group and a perfluoroethylene group, and an average of 7 perfluoromethylene groups and an average of 8 perfluoroethylene groups are present per molecule, and the number of fluorine atoms is (The average is 46.)

Example 1
A glass flask equipped with a stirrer, a thermometer, a condenser, and a dropping device was charged with 78.4 parts by mass of methyl isobutyl ketone as a solvent and heated to 105 ° C. while stirring under a nitrogen stream. Subsequently, 20 parts by mass of the compound (A-1-1) having a poly (perfluoroalkylene ether) chain obtained in Synthesis Example 1, polypropylene glycol monomethacrylate (“Blemmer PP-1000” manufactured by NOF Corporation, hydroxyl group) 382, repeating number of propylene oxide units: average 6) 99.1 parts by mass of a monomer solution obtained by dissolving 58.4 parts by mass in 40.7 parts by mass of methyl isobutyl ketone, and t-butylperoxy-2 as a radical polymerization initiator -Three kinds of dropping solutions of 31.8 parts by mass of a polymerization initiator solution in which 11.8 parts by mass of ethylhexanoate was dissolved in 26.5 parts by mass of methyl isobutyl ketone were set in separate dropping devices, respectively, Was simultaneously added dropwise over 2 hours while maintaining at 105 ° C. After completion of dropping, the mixture was stirred at 105 ° C. for 5 hours, and then a part of the solvent was distilled off under reduced pressure to obtain a polymer (P-1).

Next, 0.1 parts by mass of p-methoxyphenol as a polymerization inhibitor and 0.03 parts by mass of tin octylate as a urethanization catalyst were charged, stirring was started under an air stream, and 2-acryloyloxy was maintained while maintaining 60 ° C. 21.6 parts by mass of ethyl isocyanate was added dropwise over 1 hour. After completion of the dropwise addition, the mixture was stirred at 60 ° C. for 2 hours, then heated to 80 ° C. and stirred for 10 hours, and the disappearance of the isocyanate group was confirmed by IR spectrum measurement, and 50 fluorine-containing curable resin (1) was added. A methyl isobutyl ketone solution containing mass% was obtained. As a result of measuring the molecular weight of the obtained fluorine-containing curable resin (1) by GPC (polystyrene equivalent molecular weight), it was a number average molecular weight 2,500 and a weight average molecular weight 6,100. The fluorine content was 11% by mass. In addition, the chart figure of IR spectrum of fluorine-containing curable resin (1) is shown in FIG. 1, the chart figure of ¹³ C-NMR spectrum is shown in FIG. 2, and the chart figure of GPC is shown in FIG.

(Example 2)
A glass flask equipped with a stirrer, a thermometer, a condenser, and a dropping device was charged with 81.1 parts by mass of methyl isobutyl ketone as a solvent and heated to 105 ° C. while stirring under a nitrogen stream. Next, 30 parts by mass of the compound (A-1-1) having a poly (perfluoroalkylene ether) chain obtained in Synthesis Example 1, polypropylene glycol monomethacrylate (“Blemmer PP-1000” manufactured by NOF Corporation, hydroxyl group) 382, repeating number of propylene oxide units: average 6) 98.6 parts by mass of a monomer solution obtained by dissolving 51.1 parts by mass in 47.5 parts by mass of methyl isobutyl ketone, and t-butylperoxy-2 as a radical polymerization initiator -Three types of dropping solutions of 34.3 parts by mass of a polymerization initiator solution in which 12.2 parts by mass of ethylhexanoate was dissolved in 22.1 parts by mass of methyl isobutyl ketone were set in separate dropping devices, respectively, Was simultaneously added dropwise over 2 hours while maintaining at 105 ° C. After completion of dropping, the mixture was stirred at 105 ° C. for 5 hours, and then the solvent was distilled off under reduced pressure to obtain a polymer (P-2).

  Next, 100 parts by mass of methyl ethyl ketone as a solvent, 0.1 part by mass of p-methoxyphenol as a polymerization inhibitor, and 0.03 part by mass of tin octylate as a urethanization catalyst were added, and stirring was started under an air stream. While maintaining, 18.9 parts by mass of 2-acryloyloxyethyl isocyanate was added dropwise over 1 hour. After completion of the dropwise addition, the mixture was stirred at 60 ° C. for 2 hours, then heated to 80 ° C. and stirred for 10 hours. By confirming disappearance of the isocyanate group by IR spectrum measurement, 50 fluorinated curable resin (2) was added. A methyl ethyl ketone solution containing mass% was obtained. As a result of measuring the molecular weight of the obtained fluorine-containing curable resin (2) by GPC (polystyrene equivalent molecular weight), it was a number average molecular weight 2,600 and a weight average molecular weight 7,700. The fluorine content was 17% by mass.

(Example 3)
A glass flask equipped with a stirrer, a thermometer, a condenser, and a dropping device was charged with 73.9 parts by mass of methyl isobutyl ketone as a solvent and heated to 105 ° C. while stirring under a nitrogen stream. Next, 20 parts by mass of the compound (A-1-1) having a poly (perfluoroalkylene ether) chain obtained in Synthesis Example 1, polyethylene glycol monomethacrylate (“Blemmer PE-200” manufactured by NOF Corporation, hydroxyl group) 192, number of repeating ethylene oxide units: 4 on average 4) 91.9 parts by mass of a monomer solution obtained by dissolving 53.9 parts by mass in 38 parts by mass of methyl isobutyl ketone, and t-butylperoxy-2-ethyl as a radical polymerization initiator Three types of dripping liquid and 37 parts by mass of a polymerization initiator solution obtained by dissolving 11.1 parts by mass of hexanoate in 25.9 parts by mass of methyl isobutyl ketone were set in separate dripping apparatuses, and the flask was heated to 105 ° C. While maintaining, it was added dropwise over 2 hours. After completion of dropping, the mixture was stirred at 105 ° C. for 5 hours to obtain a polymer (P-3).

  Next, 0.1 parts by mass of p-methoxyphenol as a polymerization inhibitor and 0.03 parts by mass of tin octylate as a urethanization catalyst were charged, stirring was started under an air stream, and 2-acryloyloxy was maintained while maintaining 60 ° C. 26.1 parts by mass of ethyl isocyanate was added dropwise over 1 hour. After completion of the dropwise addition, the mixture was stirred at 60 ° C. for 2 hours, then heated to 80 ° C. and stirred for 10 hours, and the disappearance of the isocyanate group was confirmed by IR spectrum measurement. A methyl isobutyl ketone solution containing mass% was obtained. As a result of measuring the molecular weight of the obtained fluorine-containing curable resin (3) by GPC (polystyrene equivalent molecular weight), it was a number average molecular weight 2,700 and a weight average molecular weight 23,000. The fluorine content was 11% by mass.

Example 4
A glass flask equipped with a stirrer, a thermometer, a condenser, and a dropping device was charged with 78.4 parts by mass of methyl isobutyl ketone as a solvent and heated to 105 ° C. while stirring under a nitrogen stream. Next, 20 parts by mass of the compound (A-2-1) having a poly (perfluoroalkylene ether) chain obtained in Synthesis Example 2, polypropylene glycol monomethacrylate (“Blemmer PP-1000” manufactured by NOF Corporation, hydroxyl group) 382, repeating number of propylene oxide units: average 6) 100.4 parts by mass of a monomer solution obtained by dissolving 58.4 parts by mass in 42 parts by mass of methyl isobutyl ketone, and t-butylperoxy-2-ethyl as a radical polymerization initiator Three types of dripping liquids of 39.8 parts by mass of a polymerization initiator solution obtained by dissolving 11.8 parts by mass of hexanoate in 28 parts by mass of methyl isobutyl ketone were set in separate dropping devices, and the temperature in the flask was set to 105 ° C. While maintaining, it was added dropwise over 2 hours. After completion of dropping, the mixture was stirred at 105 ° C. for 5 hours to obtain a polymer (P-4).

  Next, 0.1 parts by mass of p-methoxyphenol as a polymerization inhibitor and 0.03 parts by mass of tin octylate as a urethanization catalyst were charged, stirring was started under an air stream, and 2-acryloyloxy was maintained while maintaining 60 ° C. 21.6 parts by mass of ethyl isocyanate was added dropwise over 1 hour. After completion of the dropwise addition, the mixture was stirred at 60 ° C. for 2 hours, then heated to 80 ° C. and stirred for 10 hours. By confirming disappearance of the isocyanate group by IR spectrum measurement, 40 fluorinated curable resin (4) was obtained. A methyl isobutyl ketone solution containing mass% was obtained. As a result of measuring the molecular weight of the obtained fluorine-containing curable resin (4) by GPC (polystyrene equivalent molecular weight), it was a number average molecular weight 2,500 and a weight average molecular weight 6,100. The fluorine content was 11% by mass.

(Comparative Example 1)
A glass flask equipped with a stirrer, a thermometer, a condenser, and a dropping device was charged with 100 parts by mass of methyl isobutyl ketone as a solvent and heated to 105 ° C. while stirring under a nitrogen stream. Next, 50 parts by mass of an acrylate having a fluorinated alkyl group represented by the following formula (Y-1) and 50 parts by mass of an acrylate having an ethylene oxide chain and a propylene oxide chain represented by the following formula (Y-2) are methylisobutyl. 65 parts by mass of a polymerization initiator solution in which 250 parts by mass of a monomer solution dissolved in 150 parts by mass of a ketone and 5 parts by mass of t-butylperoxy-2-ethylhexanoate as a radical polymerization initiator were dissolved in 50 parts by mass of methyl isobutyl ketone. Were dropped in 3 hours while keeping the inside of the flask at 105 ° C. After completion of the dropwise addition, the mixture was stirred at 105 ° C. for 10 hours, and then part of the solvent was distilled off under reduced pressure to obtain a methyl isobutyl ketone solution containing 50% by mass of the fluorinated copolymer (1). As a result of measuring the molecular weight of the fluorine-containing copolymer (1) (1) by GPC (polystyrene conversion molecular weight), the number average molecular weight was 4,000 and the weight average molecular weight was 10,000. The fluorine content was 32% by mass.

（式中、ｎは平均４であり、ｍは平均３である。）

(Where n is an average of 4 and m is an average of 3)

(Comparative Example 2)
A glass flask equipped with a stirrer, a thermometer, a condenser, and a dropping device was charged with 69 parts by mass of methyl isobutyl ketone as a solvent and heated to 105 ° C. while stirring under a nitrogen stream. Then, 137.8 parts by mass of a monomer solution obtained by dissolving 40 parts by mass of the fluorinated alkyl group-containing acrylate represented by the above formula (Y-1) and 28.8 parts by mass of 2-hydroxyethyl methacrylate in 69 parts by mass of methyl isobutyl ketone. And 25.9 parts by mass of a polymerization initiator solution obtained by dissolving 3.4 parts by mass of t-butylperoxy-2-ethylhexanoate in 22.5 parts by mass of methyl isobutyl ketone as a radical polymerization initiator The liquids were set in separate dropping devices, and dropped simultaneously over 3 hours while keeping the inside of the flask at 105 ° C. After completion of dropping, the mixture was stirred at 105 ° C. for 10 hours to obtain a polymer.

  Next, 0.1 parts by mass of p-methoxyphenol as a polymerization inhibitor and 0.05 parts by mass of dibutyltin dilaurate as a urethanization catalyst were charged, and 31.2 masses of 2-acryloyloxyethyl isocyanate while maintaining 60 ° C. in an air stream. The part was added dropwise over 1 hour. After completion of dropping, the mixture was stirred at 60 ° C. for 1 hour, then heated to 80 ° C. and stirred for 10 hours. As a result, disappearance of isocyanate groups was confirmed by IR spectrum measurement. Subsequently, a part of the solvent was distilled off under reduced pressure to obtain a methyl isobutyl ketone solution containing 50% by mass of the fluorine-containing curable resin (5). As a result of measuring the molecular weight of the fluorine-containing curable resin (5) by GPC (polystyrene equivalent molecular weight), the number average molecular weight was 3,000 and the weight average molecular weight was 7,000. The fluorine content was 25% by mass.

(Comparative Example 3)
A glass flask equipped with a stirrer, thermometer, condenser, and dropping device was charged with 63 parts by mass of methyl isobutyl ketone as a solvent and heated to 105 ° C. while stirring under a nitrogen stream. Next, 21.5 parts by mass of the compound (A-1-1) having a poly (perfluoroalkylene ether) chain obtained in Synthesis Example 1, 41.3 parts by mass of 2-hydroxyethyl methacrylate, and a radical polymerization initiator 3 drops of a polymerization initiator solution of 135.4 parts by mass of 9.4 parts by mass of t-butylperoxy-2-ethylhexanoate dissolved in 126 parts by mass of methyl isobutyl ketone were respectively added to separate dropping devices. The flask was added dropwise at the same time over 2 hours while keeping the inside of the flask at 105 ° C. After completion of dropping, the mixture was stirred at 105 ° C. for 10 hours, and then a part of the solvent was distilled off under reduced pressure to obtain a polymer.

  Next, 75.7 parts by mass of methyl ethyl ketone, 0.1 part by mass of p-methoxyphenol as a polymerization inhibitor, and 0.03 part by mass of tin octylate as a urethanization catalyst were added, and stirring was started under an air stream. While maintaining, 44.8 parts by mass of 2-acryloyloxyethyl isocyanate was added dropwise over 1 hour. After completion of the dropwise addition, the mixture was stirred at 60 ° C. for 1 hour, then heated to 80 ° C. and stirred for 10 hours, and the disappearance of the isocyanate group was confirmed by IR spectrum measurement, and 50 fluorine-containing curable resin (6) was added. A methyl ethyl ketone solution containing mass% was obtained. As a result of measuring the molecular weight of the obtained fluorine-containing curable resin (6) by GPC (polystyrene equivalent molecular weight), it was a number average molecular weight 2,200 and a weight average molecular weight 6,500. The fluorine content was 11% by mass.

  About the fluorine-containing curable resins (1) to (6) and the fluorine-containing copolymer (1) obtained in Examples 1 to 4 and Comparative Examples 1 to 3, the raw materials, molecular weight, and the like are summarized in Table 1. .

The abbreviations in Table 1 are as follows.
POMA: Polypropylene glycol monomethacrylate EOMA: Polyethylene glycol monomethacrylate HEMA: 2-hydroxyethyl methacrylate AOI: 2-acryloyloxyethyl isocyanate

(Preparation of base resin composition of active energy ray-curable coating composition)
125 parts by mass of UV curable urethane acrylate resin (“Unidic 17-806” manufactured by DIC Corporation; butyl acetate solution with a resin content of 80% by mass), 1-hydroxycyclohexyl phenyl ketone (Ciba Specialty Chemicals Co., Ltd.) as a photopolymerization initiator "Irgacure 184") 5 parts by weight, 54 parts by weight of toluene as a solvent, 28 parts by weight of 2-propanol, 28 parts by weight of ethyl acetate, and 28 parts by weight of propylene glycol monomethyl ether are mixed and dissolved to obtain an active energy ray-curable coating material A base resin composition of the composition was obtained.

(Examples 5-8, Comparative Examples 4-7)
The fluorine-containing curable resin solutions (1) to (6) or the fluorine-containing curable resin solutions obtained in Examples 1 to 4 and Comparative Examples 1 to 3 as fluorine-based surfactants were contained in 268 parts by mass of the base resin composition obtained above. An amount of 1 part by mass of the fluorocopolymer (1) as a resin component was added and mixed uniformly to obtain an active energy ray-curable coating composition. Next, this active energy ray-curable coating composition was applied to a bar coater No. 13 was applied to a polyethylene terephthalate (PET) film having a thickness of 188 μm, and then placed in a dryer at 60 ° C. for 5 minutes to volatilize the solvent. Next, the dried coating film was cured by irradiating with ultraviolet rays (UV) with an ultraviolet curing device (in a nitrogen atmosphere, a high pressure mercury lamp, an ultraviolet irradiation amount of ² kJ / m ² ), and Examples 5 to 8 and Comparative Examples 4 to 7 were cured. A coated film was prepared. Moreover, the coating film was similarly produced only about the base resin composition of the active energy ray hardening-type coating composition, without adding anything, and it was set as the comparative example 7.

[Evaluation of antifouling properties]
Draw a line on the coated surface of the resulting coated film with a felt-tip pen (Magic ink large black made by Teranishi Chemical Industry Co., Ltd.), and observe the adhesion state of the black ink with antifouling property (dirt adhesion) The evaluation of the prevention property and the resistance to repeated wiping of dirt was performed. The evaluation criteria are as follows.

[Evaluation criteria for dirt adhesion prevention]
AA: The antifouling property is the best and the ink repels.
A: The ink does not repel and forms a linear repelling (the line width is less than 50% of the width of the tip of the felt pen).
B: Ink repelling occurred and the line width was 50% or more and less than 100% of the width of the tip of the felt pen.
C: The ink can be drawn cleanly on the surface without repelling at all.

[Evaluation criteria for wiping off dirt]
After the above test for preventing soil adhesion, the appearance when wiped with a tissue paper under a load of 1 kg was evaluated according to the following criteria.
A: The ink can be completely removed by wiping once.
B: The ink was completely removed by wiping 2 to 10 times.
C: The ink could not be completely removed after 10 wiping operations.

[Measurement of the number of times of wiping and removing dirt]
After the above stain adhesion prevention test, wipe off all the adhered ink with tissue paper under a load of 1 kg, then draw a line again with the felt pen on the same place on the coated surface of the coated film, and remove the adhered ink from the tissue. All the paper was wiped off repeatedly, and the number of times the ink adhering until the ink no longer repels on the surface of the coating film was wiped off with a tissue paper was measured as the number of times the dirt was wiped off. Note that the maximum number of dirt wiping removals was 20 and when the ink was repelled after wiping off the adhered ink 20 times, the evaluation result was expressed as “> 20”.

[Evaluation criteria for repeated wipe resistance]
From the result of the number of times of wiping and removing the dirt measured as described above, the repeated wiping resistance against dirt was evaluated according to the following criteria.
AA: The ink was wiped and removed 20 times or more.
A: The ink was wiped and removed 10 times or more and less than 20 times.
B: The ink can be wiped and removed at least once and less than 10 times.
C: The ink could not be wiped off once.

  The evaluation results are shown in Table 2.

  Curing of the active energy ray-curable coating composition of Examples 5 to 8 to which the fluorine-containing curable resins (1) to (4) obtained in Examples 1 to 4 which are fluorine-containing curable resins of the present invention were added. It was found that the coating film has excellent dirt adhesion prevention and dirt wiping properties, and has a resistance to repeated wiping off dirt that can prevent sufficient adhesion even after repeated wiping.

  On the other hand, Comparative Example 4 using the fluorinated copolymer (1) having no curability had a slight antifouling property against ink, but was poor in stain wiping property and stain wiping repeated resistance. I found out.

  Comparative Example 5 using the fluorinated copolymer (5) having no poly (perfluoroalkylene ether) chain had good dirt adhesion prevention property, but poor dirt wiping property and dirt wiping repeated resistance. I found out.

  Comparative Example 6 using a fluorine-containing copolymer (6) having a poly (perfluoroalkylene ether) chain but not having a polyalkylene ether group as a raw material has good dirt adhesion prevention and dirt wiping properties. However, it was found that the resistance to repeated wiping of dirt was somewhat insufficient.

  It turned out that the comparative example 7 which did not add an additive is inferior to all of dirt adhesion prevention property, dirt wiping property, and dirt wiping repeated resistance.

Claims (5)

  A fluorine-containing curable resin, which is a polymer having a poly (perfluoroalkylene ether) chain, a polyalkylene ether chain and a radically polymerizable unsaturated group in the structure of the polymer.   The fluorine-containing curable resin according to claim 1, wherein the polyalkylene ether chain is a polypropylene ether chain or a polyethylene ether chain.   An active energy ray-curable coating composition comprising the fluorine-containing curable resin according to claim 1 or 2, and an active energy ray-curable resin or an active energy ray-curable monomer.   The fluorine-containing curable resin according to claim 1 or 2 or the active energy ray-curable coating composition according to claim 3 is applied to a substrate and cured by irradiation with active energy rays. Cured product.   An article having a cured coating film of the fluorine-containing curable resin according to claim 1 or 2 or the active energy ray-curable coating composition according to claim 3.

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