JP2012092308A - Fluorine-containing polymerizable resin, active energy ray-curable composition using the same, and cured product of the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a fluorine-containing polymerizable resin which can be used as a fluorine-containing surfactant to impart excellent stain-proof property and scratch resistance to a cured coating film surface, and to provide an active energy ray-curable composition which can maintain excellent stain-proof property even when the cured coating film surface has been worn by repeatedly wiping off a stain attached to the coating film surface after coating and curing, the cured product thereof, and an article having the cured coating film.SOLUTION: The fluorine-containing polymerizable resin is a polymer which is obtained by polymerizing a polymerizable unsaturated monomer and which has a poly(perfluoroalkylene ether) chain, an adamantyl group, and a polymerizable unsaturated group in the structure of the polymer. The active energy ray-curable composition is obtained by adding the fluorine-containing polymerizable resin thereto.

Description

  The present invention relates to a fluorine-containing surfactant and a fluorine-containing polymerizable resin used as a fluorine-containing surface modifier capable of imparting excellent antifouling properties, liquid repellency, and scratch resistance to a coating film surface. The present invention also relates to an active energy ray-curable composition using the fluorine-containing polymerizable resin, a cured product thereof, and an article having the cured coating film.

  Conventionally, a front protective plate is further provided on a polarizing plate which is the outermost surface of a liquid crystal display. As the front protective plate, a transparent resin plate (acrylic (PMMA) sheet, polycarbonate (PC) sheet, PMMA / PC composite type sheet) or glass is used. Since the resin sheet has a thickness of 0.3 mm to 2 mm and is softer than glass and is likely to be scratched by scratching, a hard coat layer is provided on the surface to provide scratch resistance.

  As a method for improving the scratch resistance by providing the above hard coat layer, a cured coating film obtained by curing a hard coat material containing a polyfunctional monomer such as a polyfunctional (meth) acrylate is used as a base material surface. The method of forming is known. However, the conventional cured coating film has a problem in that when dirt such as fingerprints, sebum, sweat, and cosmetics adheres, the dirt is conspicuous and the screen display is difficult to see. In addition, in order to make the screen display easier to see, it is not easy to remove the dirt.

  Therefore, in order to prevent the adhesion of dirt, and to impart antifouling properties that can easily remove the attached dirt, the hard coat material may be combined with a fluorine-containing surfactant or fluorine-containing surface modifier (hereinafter, these are also combined). Studies have been made to simply add “fluorinated surfactant”) as an additive. In particular, in order to maintain antifouling properties, a monoacrylate having a polymerizable group, a monoacrylate having a fluorinated alkyl group designed to be immobilized by a covalent bond in a cured coating film, and an acrylic monomer having active hydrogen. A polymerizable fluorine-containing surfactant having an unsaturated group obtained by copolymerizing with a monomer and then reacting the obtained polymer with an acrylic monomer having an isocyanate group has been proposed (for example, , See Patent Document 1). This polymerization type fluorine-containing surfactant has a polymerizable group, and when used as an additive to a hard coat material, it is bonded to the polymerization component in the composition by a covalent bond and fixed to the coating film. The However, there has been a problem that the antifouling property is lowered when the surface of the cured coating film of the hard coat material is repeatedly wiped many times to wear the coating film surface. In addition, there is a problem that the surface of the cured coating film is easily damaged when worn with steel wool or the like.

  In addition, a poly (perfluoroalkylene ether) chain produced from a compound having a (perfluoroalkylene ether) chain and having di (meth) acryloyl groups at both ends thereof, and a polymerizable fluorine-containing group having an unsaturated group A surfactant has been proposed (for example, see Patent Document 2). Similar to the one described in Patent Document 1, the polymerization-type fluorine-containing surfactant also has a problem that the antifouling property after wear is greatly reduced, and when the surface of the cured coating film is worn with steel wool or the like, it is easily damaged.

  Therefore, in order to wipe off dirt repeatedly adhered, there has been a demand for a material that maintains antifouling properties even when the coating film surface is worn and has high scratch resistance.

JP 2007-246696 A International Publication WO2009 / 133770

  The problem to be solved by the present invention is to provide a fluorine-containing polymerizable resin that can impart excellent antifouling properties and scratch resistance to the surface of a cured coating film and can be used as a fluorine-containing surfactant. It is. In addition, after coating and curing, dirt that adheres to the surface of the cured coating film is repeatedly wiped off to maintain excellent antifouling properties and have excellent scratch resistance even when the cured coating surface is worn. An active energy ray-curable composition that provides a coating film, 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, an adamantyl group and a polymerizable unsaturated group in the structure of the polymer, and the polymer The active energy ray-curable composition containing a coalescence can impart excellent antifouling properties to the cured coating surface, and even if the coating surface is repeatedly wiped off and the coating surface is worn, it is excellent. It was found that the antifouling property can be maintained, and the present invention has been completed.

  That is, the present invention is a polymer obtained by polymerizing a polymerizable unsaturated monomer, wherein a poly (perfluoroalkylene ether) chain, an adamantyl group and a polymerizable unsaturated group are contained in the structure of the polymer. The present invention relates to a fluorine-containing polymerizable resin characterized by being a polymer having an active energy ray-curable composition using the same.

  Furthermore, the present invention provides a cured product obtained by applying the fluorinated polymerizable resin or active energy ray-curable composition to a substrate and irradiating and curing the active energy ray, and the fluorinated polymerizable resin or activity. The present invention relates to an article having a cured coating film of an energy beam curable composition.

  The fluorine-containing polymerizable resin of the present invention can impart antifouling properties to the surface of the substrate by applying it alone to a substrate to form a cured coating film. In addition, the active energy ray-curable composition added with the fluorine-containing polymerizable resin as a fluorine-containing surfactant has the effect of minimizing the surface free energy peculiar to fluorine atoms when applied to a substrate. Thus, the polymerizable fluorine-based compound is segregated on the surface of the coating film, and surface modification that imparts antifouling property or the like only to the coating film surface is possible. Furthermore, since the fluorine-containing polymerizable resin can be polymerized with other curable components in the active energy ray-curable composition, the polymerizable fluorine-based compound of the present invention is stronger in the cured coating film. Therefore, volatilization and desorption of the polymerizable fluorine-based compound or a decomposition product thereof can be suppressed from the surface of the cured coating film even if heat treatment, washing or the like is performed.

  Moreover, the cured coating film using the fluorine-containing polymerizable resin of the present invention has excellent antifouling properties on the surface, and repeatedly wipes off the dirt adhering to the surface of the cured coating film. Even if the surface is worn, the excellent antifouling property can be maintained, so that it is extremely useful as a hard coat layer for a front protective plate provided on the outermost surface of the liquid crystal display.

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

  The fluorine-containing polymerizable resin of the present invention is a polymer obtained by polymerizing a polymerizable unsaturated monomer, and includes a poly (perfluoroalkylene ether) chain, an adamantyl group and a polymer in the structure of the polymer. It is a fluorine-containing polymerizable resin characterized by being a polymer having a polymerizable unsaturated group.

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

(Manufacturing method 1)
A poly (perfluoroalkylene ether) chain, a compound (A) having a polymerizable unsaturated group at both ends thereof, a polymerizable unsaturated monomer (B1) having an adamantyl group having a reactive functional group (b1), A compound (C) having a polymerizable unsaturated group and a functional group (c) having a reactivity with the functional group (b1) to a polymer (P1) obtained by copolymerizing as an essential monomer component ).

(Manufacturing method 2)
A poly (perfluoroalkylene ether) chain, a compound (A) having a polymerizable unsaturated group at both ends thereof, and a polymerizable unsaturated monomer (B1) having an adamantyl group having a reactive functional group (b1) or A polymerizable unsaturated monomer (B2) having an adamantyl group having no reactive functional group (b1) and a polymerizable unsaturated monomer (B3) having a reactive functional group (b3) The polymer (P2) obtained by copolymerization as a monomer component has a functional group (c) having a reactivity with the functional group (b1) or the functional group (b3) and a polymerizable unsaturated group. A method of reacting one or more compounds (C).

  Next, each raw material used for manufacture of said fluorine-containing polymeric resin of this invention is demonstrated.

  In the production methods 1 and 2, the poly (perfluoroalkylene ether) chain and the compound (A) having a polymerizable unsaturated group at both ends thereof as a raw material for the fluorine-containing polymerizable resin of the present invention 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（ａ１）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 (a1), 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 a ratio of 1/10 to 10/1 from the viewpoint of antifouling properties. The value of n in the structural formula (a1) is preferably in the range of 3 to 100, more preferably in the range of 6 to 70, and more preferably in the range of 12 to 50.

  The poly (perfluoroalkylene ether) chain is a poly (perfluoroalkylene ether) chain 1 because it has excellent antifouling properties and slipperiness and can easily 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 introducing a polymerizable unsaturated group at both ends as a raw material of the compound (A). In the following structural formulas, “—PFPE—” represents the poly (perfluoroalkylene ether) chain.

  Examples of the polymerizable unsaturated group at both ends of the chain of the compound (A) include those having a polymerizable unsaturated group represented by the following structural formulas U-1 to U-5.

  Among these polymerizable unsaturated groups, in particular, the availability of the compound (A) itself and the ease of production, or the point of excellent polymerizability with the polymerizable unsaturated monomers (B1) to (B3) described later, The acryloyloxy group represented by Structural Formula U-1 and the methacryloyloxy group represented by Structural Formula U-2 are preferable. Moreover, since chemical resistance improves, the methacryloyloxy group represented by Structural formula U-2 and the styryl methoxy group represented by Structural formula U-5 are preferable.

  Examples of the compound (A) having the acryloyloxy group described above include those represented by the following structural formulas (A-1) to (A-13). 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. Moreover, since chemical resistance improves, the said structural formula (A-2), (A-4), (A-12), (A-13) is preferable.

  In order to produce the compound (A), for example, a compound having one hydroxyl group at both ends of a poly (perfluoroalkylene ether) chain is subjected to dehydrochlorination reaction with (meth) acrylic acid chloride or chloromethylstyrene. 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) For compounds having a cyanate group one by one, and a method of reacting a 2-hydroxyethyl acrylamide. Among these, a method obtained by dehydrochlorinating (meth) acrylic acid chloride or chloromethylstyrene with respect to a compound having one hydroxyl group at both ends of a poly (perfluoroalkylene ether) chain; A method obtained by subjecting (meth) acryloyloxyethyl 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 polymeric resin of this invention in the said manufacturing method 1 is demonstrated. The adamantyl group of the monomer (B1) is an organic group having the following adamantane structure.

  Examples of the reactive functional group (b1) possessed by the adamantyl group of the monomer (B1) include a hydroxyl group, an isocyanate group, an epoxy group, a carboxyl group, a carboxylic acid halide group, and an acid anhydride group. The polymerizable unsaturated group possessed by the monomer (B1) is preferably a carbon-carbon unsaturated double bond having radical polymerizability, more specifically, a vinyl group, a (meth) acryloyl group, a maleimide group, or the like. (Meth) acryloyl group is more preferable from the viewpoint of easy polymerization. These monomers (B1) can be used alone or in combination of two or more different reactive functional groups (b1) and polymerizable unsaturated groups.

  As said monomer (B1) which has a (meth) acryloyl group as a polymerizable unsaturated group, the compound represented by the following general formula (B1-1) is mentioned, for example.

（式中、Ｌは前記反応性官能基（ｂ１）を表し、Ｘ及びＹは２価の有機基又は単結合を表し、Ｒは水素原子、メチル基又はＣＦ_３を表す。）

(In the formula, L represents the reactive functional group (b1), X and Y represent a divalent organic group or a single bond, and R represents a hydrogen atom, a methyl group, or CF ₃ ).

  The bonding position of Y and the organic group having the reactive functional group (b1) represented by -XL in the general formula (B1-1) is bonded to any carbon atom in the adamantane structure. Moreover, you may have 2 or more about -XL. Furthermore, part or all of the hydrogen atoms bonded to the carbon atoms constituting the adamantane structure may be substituted with fluorine atoms, alkyl groups, or the like. In the general formula (B1-1), X and Y are a divalent organic group or a single bond. Examples of the divalent organic group include carbon atoms such as a methylene group, a propyl group, and an isopropylidene group. The alkylene group of number 1-8 is mentioned.

  More specific examples of the monomer (B1) include compounds represented by the following formulas (B1-1-1) to (B1-1-5).

  The said monomer (B2) used as the raw material of the fluorine-containing polymeric resin of this invention in the said manufacturing method 2 is demonstrated. The monomer (B2) is a polymerizable unsaturated monomer having an adamantyl group, and the adamantyl group is the same as the monomer (B1). The polymerizable unsaturated group of the monomer (B2) is preferably a carbon-carbon unsaturated double bond having radical polymerizability, and more specifically, a vinyl group, a (meth) acryloyl group, a maleimide. A (meth) acryloyl group is more preferable from the viewpoint of easy polymerization. These monomers (B2) can be used alone or in combination of two or more.

  As said monomer (B2) which has a (meth) acryloyl group as a polymerizable unsaturated group, the compound represented by the following general formula (B2-1) is mentioned, for example.

（式中、Ｒは水素原子、メチル基又はＣＦ_３を表す。）

(In the formula, R represents a hydrogen atom, a methyl group or CF _3. )

  The (meth) acryloyl group may be bonded to any carbon atom in the adamantane structure. Moreover, the hydrogen atom couple | bonded with the carbon atom which comprises the adamantane structure in the said general formula (B2-1) may substitute the one part or all part by the fluorine atom, the alkyl group, etc.

  More specific examples of the monomer (B2) include compounds represented by the following formulas (B2-1-1) to (B2-1-3).

  In the production method 2, the monomer (B3) serving as a raw material for the fluorine-containing polymerizable resin of the present invention will be described. Examples of the reactive functional group (b3) of the monomer (B3) include a hydroxyl group, an isocyanate group, an epoxy group, a carboxyl group, a carboxylic acid halide group, and an acid anhydride group. The polymerizable unsaturated group of the monomer (B3) is preferably a carbon-carbon unsaturated double bond having radical polymerizability, and more specifically, a vinyl group, a (meth) acryloyl group, a maleimide. 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, lactone modified with a hydroxyl group at the terminal (meth) Unsaturated monomer having hydroxyl group such as acrylate; 2- (meth) acryloyloxyethyl isocyanate, 2- (2- (meth) acryloyloxyethoxy) ethyl isocyanate, 1,1-bis ((meth) acryloyloxymethyl) Unsaturated monomers having an isocyanate group such as ethyl isocyanate; unsaturated monomers having an epoxy group such as glycidyl methacrylate and 4-hydroxybutyl acrylate glycidyl ether; (meth) acrylic acid, 2- (meth) acryloyloxyethyl Unsaturated monomers having a carboxyl group such as succinic acid, 2- (meth) acryloyloxyethylphthalic acid, maleic acid and itaconic acid; acid anhydrides having an unsaturated double bond such as maleic anhydride and itaconic anhydride Etc. These monomers (B3) can be used alone or in combination of two or more.

  Moreover, in the said manufacturing method 1 or 2, when manufacturing the said polymer (P1) or (P2) which is an intermediate body of the fluorine-containing polymerizable resin of this invention, the said compound (A), monomer (B1) In addition to the monomer (B2) and the monomer (B3), other polymerizable unsaturated monomers (B4) that can be copolymerized therewith may be used. Examples of such other polymerizable unsaturated monomer (B4) include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl (meth). Acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, n-heptyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl ( (Meth) acrylates such as (meth) acrylate, dodecyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, (meth) acrylate having a polyoxyalkylene chain; styrene, α-methylstyrene, p -Methyls Aromatic vinyls such as len and p-methoxystyrene; maleimides such as maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, cyclohexylmaleimide, etc. Can be mentioned.

  In the said manufacturing method 1 or 2, the said compound (C) used as the raw material of the fluorine-containing polymeric resin of this invention is demonstrated. Examples of the functional group (c) that the compound (C) has include a hydroxyl group, an isocyanate group, an epoxy group, a carboxyl group, a carboxylic acid halide group, and an acid anhydride. When the reactive functional group (b1) or (b3) possessed by the monomer (B1) or (B3) is a hydroxyl group, the functional group (c) is an isocyanate group, a carboxyl group, a carboxylic acid halide group, an epoxy When the reactive functional group (b1) or (b3) is an isocyanate group, the functional group (c) includes a hydroxyl group, and the reactive functional group (b1) or (b3) is an epoxy group. Is a carboxyl group and a hydroxyl group as the functional group (c), and when the reactive functional group (b1) or (b3) is a carboxyl group, the functional group (c) is an epoxy group or a hydroxyl group. Is mentioned.

  Here, in the production method 2, when the monomer (B1) and the monomer (B3) are used in combination, the reactive functional group (b1) and the reactive functional group (b3) included in these monomers are In the case of different functional groups, and when the reactive functional groups (b1) and (b3) react with a common functional group, the reactivity with the reactive functional groups (b1) and (b3) is increased. One type of compound (C) having the functional group (c) can be used. In addition, when the reactive functional group (b1) and the reactive functional group (b3) do not react with a common functional group, a compound having a functional group (c) having reactivity with the reactive functional group (b1) ( It is preferable to use two or more compounds (C) such as C) and a compound (C) having a functional group (c) having reactivity with the reactive functional group (b3).

  The 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, and the like. (Meth) acryloyl groups are more preferred 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, lactone-modified (meth) acrylate having a hydroxyl group at the terminal Unsaturated monomer having a hydroxyl group such as relate; 2- (meth) acryloyloxyethyl isocyanate, 2- (2- (meth) acryloyloxyethoxy) ethyl isocyanate, 1,1-bis ((meth) acryloyloxymethyl) Unsaturated monomers having an isocyanate group such as ethyl isocyanate; unsaturated monomers having an epoxy group such as glycidyl methacrylate and 4-hydroxybutyl acrylate glycidyl ether; (meth) acrylic acid, 2- (meth) acryloyloxyethyl Unsaturated monomers having a carboxyl group such as succinic acid, 2- (meth) acryloyloxyethylphthalic acid, maleic acid and itaconic acid; acid anhydrides having an unsaturated double bond such as maleic anhydride and itaconic anhydride Etc. Moreover, 2-hydroxy-3-acryloyloxypropyl methacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate etc. can also be used as what has a several 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, 1,1-bis (acryloyloxymethyl) ethyl isocyanate 4-hydroxybutyl acrylate glycidyl ether Acrylic acid is preferred.

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

  In the production method 1 or 2, in the production method 1, the method for producing the polymer (P1) or (P2) that is an intermediate of the fluorine-containing polymerizable resin of the present invention is the compound (A) and In the case of the production method 2, the monomer (B1), the other polymerizable unsaturated monomer (B4), if necessary, the compound (A), the monomer (B1), the single monomer A method of polymerizing the monomer (B2), the monomer (B3), and, if necessary, another polymerizable unsaturated monomer (B4) in an organic solvent using a polymerization initiator is mentioned. It is done. 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 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.

  In the production method 1 or 2, the polymer (P1) or (P2) obtained as described above is reacted with the functional group (c) having a reactivity with the functional group (b1) or (b3) and polymerization. The fluorine-containing polymerizable resin of the present invention can be obtained by reacting the compound (C) having a polymerizable unsaturated group.

  The method of reacting the compound (C) with the polymer (P1) or (P2) may be performed under the condition that the polymerizable unsaturated group of the compound (C) or the like is not polymerized. It is preferable to adjust the reaction within a range of ˜120 ° C. 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 (b1) or (b3) is a hydroxyl group and the functional group (c) is an isocyanate group, p-methoxyphenol, hydroquinone, 2,6-di-t is used as a polymerization inhibitor. -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 ° C. The method of making it react with is preferable. When the functional group (b1) or (b3) is an epoxy group and the functional group (c) is a carboxyl group, or the functional group (b1) or (b3) is a carboxyl group When the functional group (c) is an epoxy group, p-methoxyphenol, hydroquinone, 2,6-di-t-butyl-4-methylphenol or the like is used as a polymerization inhibitor, and the esterification reaction catalyst is used. Reaction temperature using tertiary amines such as triethylamine, quaternary ammoniums such as tetramethylammonium chloride, tertiary phosphines such as triphenylphosphine, quaternary phosphoniums such as tetrabutylphosphonium chloride, etc. It is preferable to make it react at 80-130 degreeC, especially 100-120 degreeC.

  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 polymerizable resin of the present invention obtained as described above has excellent antifouling properties, its number average molecular weight (Mn) is preferably in the range of 1,000 to 5,000, A range of 400 to 4,000 is more preferable. The weight average molecular weight (Mw) is preferably in the range of 2,000 to 50,000, more preferably in the range of 3,000 to 20,000. These number average molecular weight (Mn) and weight average molecular weight (Mw) can be determined by the above GPC measurement.

  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: 1.0 mass% tetrahydrofuran solution filtered in terms of resin solids with a microfilter (5 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 addition, the fluorine content in the fluorine-containing polymerizable resin of the present invention is preferably in the range of 1 to 50% by mass because both antifouling properties and compatibility with other components can be achieved. The range of 35% by mass is more preferable, and the range of 10 to 25% by mass is more preferable. The fluorine content in the fluorine-containing polymerizable resin of the present invention is calculated from the mass ratio of fluorine atoms to the total amount of raw materials used.

  Furthermore, since the polymerizable unsaturated group equivalent in the fluorine-containing polymerizable resin of the present invention is excellent in scratch resistance of the cured coating film, it is 200 to 3,500 g / eq. The range of 250 to 2,000 g / eq. The range of 300-1500 g / eq. Is more preferable, 400-1,000 g / eq. The range of is particularly preferable.

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

  The active energy ray curable composition of the present invention is obtained by adding the fluorine-containing polymerizable resin of the present invention, and the main component thereof is an active energy ray curable resin (D) or active energy ray curable. Contains monomer (E). In the active energy ray-curable 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. Moreover, it is preferable to use the fluorine-containing polymerizable resin of the present invention as a fluorine-based surfactant in the active energy ray-curable composition.

  The active energy ray-curable resin (D) is a urethane (meth) acrylate resin, an unsaturated polyester resin, an epoxy (meth) acrylate resin, a polyester (meth) acrylate resin, an acrylic (meth) acrylate resin, or a resin having a maleimide group. 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 (meth) acrylate compound having a hydroxyl group. Is mentioned.

  Examples of the aliphatic polyisocyanate compound include tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, 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, hydrogenated xylile Examples include diisocyanate, hydrogenated tetramethylxylylene diisocyanate, cyclohexyl diisocyanate, and the aromatic polyisocyanate compound includes tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, xylylene diisocyanate, 1,5-naphthalene diisocyanate, Examples include toridine diisocyanate and p-phenylene diisocyanate.

  On the other hand, examples of the acrylate compound having a hydroxyl group 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) acrylate Mono- or di (meth) acrylates of trivalent alcohols such as relate, bis (2- (meth) acryloyloxyethyl) hydroxyethyl isocyanurate, or hydroxyl groups obtained by modifying some of these alcoholic hydroxyl groups with ε-caprolactone Mono- and di (meth) acrylates having a monofunctional hydroxyl group and tri- or more functional (meth) acryloyl such as pentaerythritol tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, etc. A compound having a group, or a polyfunctional (meth) acrylate having a hydroxyl group obtained by modifying the compound with ε-caprolactone; dipropylene glycol mono (meth) acrylate, diethylene glycol mono (meth) acrylate, poly (Meth) acrylate compounds having an oxyalkylene chain such as propylene 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 between the aliphatic polyisocyanate compound or the aromatic polyisocyanate compound and the acrylate compound having a hydroxyl group can be performed 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 (meth) acrylate compound having a hydroxyl group 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.

  The resin having a maleimide group includes a bifunctional maleimide urethane compound obtained by urethanizing N-hydroxyethylmaleimide and isophorone diisocyanate, and a bifunctional maleimide ester compound obtained by esterifying maleimide acetic acid and polytetramethylene glycol. Examples thereof include tetrafunctional maleimide ester compounds obtained by esterification of maleimidocaproic acid and a tetraethylene oxide adduct of pentaerythritol, and polyfunctional maleimide ester compounds obtained by esterification of maleimide acetic acid and a polyhydric alcohol compound. 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 composition of the present invention, when the fluorine-containing polymerizable 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 beam. The range of 0.01-20 mass parts is preferable with respect to a total of 100 mass parts of the curable monomer (E), more preferably 0.1-15 mass parts, and 0.5-10 mass parts. A range is further preferred. If the amount of the fluorine-containing polymerizable resin of the present invention is in this range, the leveling property, water / oil repellency and antifouling property can be made sufficient, and the hardness and transparency after curing of the composition Can also be sufficient. In addition, in the case of a thick film, the ratio of the fluorine-containing polymerizable resin of the present invention in the surface layer portion of the coating film changes depending on the film thickness when the active energy ray-curable composition of the present invention is formed into a coating film. The amount of the fluorine-containing polymerizable resin of the present invention is set low, and in the case of a thin film, the amount of the fluorine-containing polymerizable resin of the present invention is set high, so that Fluoropolymerizable resins can be uniformly present, and high scratch resistance can be expected, which is preferable.

  The fluorine-containing polymerizable resin or active energy ray-curable 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 polymerizable 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 composition is excellent. Therefore, 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 composition of the present invention is not limited to the effects of the present invention, depending on the purpose of use, characteristics, etc. Various compounding materials for the purpose of adjusting coating properties and coating film properties, such as 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, various organic or inorganic particles such as PTFE (polytetrafluoroethylene), polyethylene, polypropylene, carbon, titanium oxide, alumina, copper, silica fine particles, polymerization initiation Agent, polymerization inhibitor, antistatic agent, antifoaming agent, viscosity modifier, light resistance stabilizer, weather resistance stabilizer, heat resistance Fixing agent, antioxidant, rust inhibitor, slip agent, wax, gloss adjuster, mold release agent, compatibilizer, conductivity modifier, pigment, dye, dispersant, dispersion stabilizer, silicone-based, hydrocarbon-based interface An activator 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 composition of the present invention. In particular, in order to perform thin film coating, the film thickness can be adjusted. It 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, although the usage-amount of an organic solvent changes with uses, the target film thickness, or viscosity, it is preferable that it is the range of 0.5-50 times amount on the mass reference | standard with respect to the total mass of a hardening component. .

  As described above, the active energy rays for curing the active energy ray-curable composition of the present invention are ionizing radiations such as ultraviolet rays, electron beams, α rays, β rays, and γ rays. Or as a curing device, for example, a germicidal lamp, an ultraviolet fluorescent lamp, a carbon arc, a xenon lamp, a high-pressure mercury lamp for copying, a medium or high-pressure mercury lamp, an ultra-high pressure mercury lamp, an electrodeless lamp, a metal halide lamp, natural light, etc. Examples of the electron beam include ultraviolet rays, a scanning type, and a 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 composition of the present invention varies depending on the application. For example, a gravure coater, roll coater, comma coater, knife coater, air knife coater, curtain coater, kiss coater, shower coater, wheeler coater, spin coater , Coating methods using dipping, screen printing, spraying, applicators, bar coaters, etc., or molding methods using various molds.

  The cured coating film of the fluorine-containing polymerizable resin of the present invention has excellent antifouling properties (ink repellency, fingerprint resistance, etc.), scratch resistance, etc. It is possible to impart antifouling properties and slipperiness to the surface. In addition, since the fluorine-containing polymerizable resin of the present invention can add leveling properties to the coating material by adding it as a fluorine-based surfactant or a fluorine-based surface modifier to the coating material, The active energy ray curing agent composition has high leveling properties.

  As an article that can impart antifouling property and slipperiness to the surface using the fluorine-containing polymerizable resin or active energy ray-curable composition of the present invention, a film for polarizing plate of a liquid crystal display (LCD) such as a TAC film Various display screens such as plasma display (PDP) and organic EL display; touch panel; housing or screen of electronic terminal such as mobile phone; transparent protective film for liquid crystal display color filter (hereinafter referred to as “CF”); liquid crystal Organic insulating film for TFT array; inkjet ink for forming electronic circuit; optical recording medium such as CD, DVD, Blu-ray disc; transfer film for insert mold (IMD, IMF); rubber roller for OA equipment such as copier, printer; Glass surface of the reading section of OA equipment such as a scanner or scanner; Optical lenses such as cameras and glasses; Windshields for watches such as watches; Glass surfaces; Windows for various vehicles such as automobiles and railway vehicles; Cover glass or film for solar cells; Various building materials such as decorative panels; Woodworking materials such as, artificial and synthetic leather, various plastic molded products such as housings for home appliances, FRP bathtubs and the like. By applying the fluorine-containing polymerizable resin or active energy ray-curable 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, antifouling properties are formed on the article surfaces. And slipperiness can be imparted. Moreover, it is also possible to add antifouling property and slipperiness to the article surface by adding the fluorine-containing polymerizable resin of the present invention to various paints suitable for each article, and applying and drying.

  In addition, the coating material in which the fluorine-containing polymerizable resin of the present invention is added to the active energy ray-curable composition improves leveling properties, and also provides antifouling properties (ink repellency) and slipping properties (scratch resistance) on the coating film surface. Property). Examples of such a coating material include a hard coat material for an LCD polarizing plate such as a TAC film, an anti-glare (AG) anti-glare coating material, or an anti-reflection (LR) coating material; a plasma display (PDP), and an organic EL display. Hard coating material for various display screens such as: Hard coating material for touch panel; Color resist for forming each pixel of RGB used for CF used in imaging elements such as liquid crystal display, organic EL display, CCD, CMOS, etc. , Printing ink, inkjet ink or paint; black resist for CF black matrix, printing ink, inkjet ink or paint; resin composition for pixel partition such as plasma display (PDP), organic EL display; electronic terminal such as mobile phone Paint for housing Hard coat material for screens of electronic terminals such as mobile phones; Transparent protective film paint for protecting the CF surface; Liquid crystal TFT array organic insulation film paint; Electronic circuit forming inkjet ink; CD, DVD, Blu-ray disc Hard coating materials for optical recording media such as: Hard coating materials for transfer films for insert molds (IMD, IMF); Coating materials for rubber rollers for OA equipment such as copying machines and printers; Reading of OA equipment such as copying machines and scanners Coating materials for glass in parts; Coating materials for optical lenses such as cameras, video cameras and glasses; Windshields for watches such as watches; Coating materials for glass; Coating materials for windows of various vehicles such as automobiles and railway vehicles; Cover glass or anti-reflective coating for film; printing ink or paint for various building materials such as decorative boards; housing Window glass for coating materials; wood paints furniture; artificial, synthetic leather for coating material; consumer electronics enclosure such as various plastic article for paint or coating material; and FRP tub paint or coating material and the like.

  Furthermore, as an article that can impart antifouling property and slipperiness to the surface using the fluorine-containing polymerizable resin or active energy ray-curable composition of the present invention, a prism sheet or a diffusion sheet that is a backlight member of LCD Etc. Further, by adding the fluorine-containing polymerizable 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 fluorine-containing polymerizable 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 polymerizable 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 polymerizable resin or active energy ray-curable composition of the present invention can be used, optical fiber cladding materials, waveguides, liquid crystal panel sealing materials, various optical sealing materials, optical Adhesives and the like.

  In particular, when the active energy ray-curable 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 resin Excellent anti-glare properties by blending inorganic or organic fine particles such as 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 composition of the present invention. Since it becomes a thing, it is preferable.

  In addition, when the fluorine-containing polymerizable resin or active energy ray-curable composition of the present invention is used for an antiglare coating material for a protective film of a polarizing plate for LCD, it is applied to a mold having an uneven surface shape before the coating material is cured. After the contact, it can be applied to a transfer method in which an active energy ray is irradiated and cured from the side opposite to the mold, and the surface of the coating film is embossed to impart an antiglare property. In addition, a transfer method in which the surface of the coating film is mirrored by irradiating with an active energy ray from the opposite side of the mold or film after contacting the mold or film having a mirror surface before curing the coating material. It can also be applied to.

Hereinafter, the present invention will be described in more detail with reference to specific examples. In addition, the measurement conditions of IR spectrum, < ¹³ > C-NMR spectrum, and GPC of the obtained fluorine-containing polymerizable resin 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: 1.0 mass% tetrahydrofuran solution filtered in terms of resin solids with a microfilter (5 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 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. .

（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.)

  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 100 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-2-1) having a poly (perfluoroalkylene ether) chain obtained in Synthesis Example 1 and 3-hydroxy-1-adamantyl methacrylate (the above formula (B1-1-1)) And a monomer solution obtained by dissolving 50.1 parts by mass in 120 parts by mass of methyl isobutyl ketone and 10.5 parts by mass of t-butylperoxy-2-ethylhexanoate as a polymerization initiator. Three types of dropping solutions with the polymerization initiator solution dissolved in parts by mass were set in separate dropping devices, and dropped simultaneously over 2 hours while maintaining the inside of the flask at 105 ° C. After completion of dropping, the mixture was stirred at 105 ° C. for 5 hours, and then 262.1 parts by mass of the solvent was distilled off under reduced pressure to obtain a polymer (P1-1) solution.

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 into the polymer (P1-1) solution obtained above, and under an air stream. Stirring was started, and 29.9 parts by mass of 2-acryloyloxyethyl isocyanate was added dropwise over 1 hour while maintaining 60 ° C. 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, thereby confirming the disappearance of the isocyanate group by IR spectrum measurement, and adding 53.7 parts by mass of methyl isobutyl ketone. A methyl isobutyl ketone solution containing 50% by mass of the fluorine-containing polymerizable resin (1) was obtained. As a result of measuring the molecular weight of the obtained fluorine-containing polymerizable resin (1) by GPC (polystyrene equivalent molecular weight), it was a number average molecular weight 1,500 and a weight average molecular weight 3,900. The fluorine-containing polymerizable resin (1) has a fluorine content of 11% by mass and a polymerizable unsaturated group equivalent of 476 g / eq. Met. 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 77.6 parts by mass of methyl isobutyl ketone as a solvent and heated to 105 ° C. while stirring under a nitrogen stream. Next, 40 parts by mass of the compound (A-2-1) having a poly (perfluoroalkylene ether) chain obtained in Synthesis Example 1 and 37.6 parts by mass of 3-hydroxy-1-adamantyl methacrylate were added to methyl isobutyl ketone 139. Three types of solutions, a monomer solution dissolved in parts by mass and a polymerization initiator solution in which 11.7 parts by mass of t-butylperoxy-2-ethylhexanoate as a polymerization initiator were dissolved in 16.2 parts by mass of methyl isobutyl ketone The dripping liquids were set in separate dripping apparatuses, respectively, and dropped simultaneously over 2 hours while maintaining the inside of the flask at 105 ° C. After completion of dropping, the mixture was stirred at 105 ° C. for 5 hours, and then 190.8 parts by mass of the solvent was distilled off under reduced pressure to obtain a polymer (P1-2) solution.

  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 into the polymer (P1-2) solution obtained above, and under an air stream Stirring was started, and 22.3 parts by mass of 2-acryloyloxyethyl isocyanate was added dropwise over 1 hour while maintaining 60 ° C. 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 to confirm the disappearance of the isocyanate group by IR spectrum measurement, and 48.7 parts by mass of methyl isobutyl ketone was added. A methyl isobutyl ketone solution containing 50% by mass of the fluorinated curable resin (2) 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 1,800 and a weight average molecular weight 5,400. The fluorine-containing polymerizable resin (2) has a fluorine content of 22% by mass and a polymerizable unsaturated group equivalent of 640 g / eq. Met.

(Example 3)
A glass flask equipped with a stirrer, a thermometer, a condenser, and a dropping device was charged with 66.3 parts by mass of methyl isobutyl ketone as a solvent and heated to 105 ° C. while stirring under a nitrogen stream. Next, 10 parts by mass of the compound (A-2-1) having a poly (perfluoroalkylene ether) chain obtained in Synthesis Example 1 and 56.3 parts by mass of 3-hydroxy-1-adamantyl methacrylate were added to methyl isobutyl ketone 122. 3 parts of a monomer solution dissolved in 6 parts by mass and a polymerization initiator solution in which 9.9 parts by mass of t-butylperoxy-2-ethylhexanoate was dissolved in 10 parts by mass of methyl isobutyl ketone as a polymerization initiator. The dripping liquids were set in separate dripping apparatuses, respectively, and dropped simultaneously over 2 hours while maintaining the inside of the flask at 105 ° C. After completion of the dropwise addition, the mixture was stirred at 105 ° C. for 5 hours, and then 154.7 parts by mass of the solvent was distilled off under reduced pressure to obtain a polymer (P1-3) solution.

  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 into the polymer (P1-3) solution obtained above, and under an air stream Stirring was started, and 33.7 parts by mass of 2-acryloyloxyethyl isocyanate was added dropwise over 1 hour while maintaining 60 ° C. 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 to confirm the disappearance of the isocyanate group by IR spectrum measurement, and 56.3 parts by mass of methyl isobutyl ketone was added. A methyl isobutyl ketone solution containing 50% by mass of the fluorinated curable resin (3) was obtained. As a result of measuring the molecular weight of the obtained fluorinated curable resin (3) by GPC (polystyrene equivalent molecular weight), it was a number average molecular weight 1,700 and a weight average molecular weight 5,000. The fluorine-containing polymerizable resin (2) has a fluorine content of 5.6% by mass, and the polymerizable unsaturated group equivalent is 420 g / eq. Met.

Example 4
A glass flask equipped with a stirrer, thermometer, condenser, and dropping device was charged with 35 parts by mass of methyl isobutyl ketone as a solvent, and the temperature was raised 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 1 and 50.1 parts by mass of 3-hydroxy-1-adamantyl methacrylate were added to methyl isobutyl ketone 84. 3 of a monomer solution dissolved in 6 parts by mass and a polymerization initiator solution in which 10.6 parts by mass of t-butylperoxy-2-ethylhexanoate as a polymerization initiator was dissolved in 10.6 parts by mass of methyl isobutyl ketone Each type of dropping liquid was set in a separate dropping apparatus, and dropped simultaneously 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 5 hours, and then 83.5 parts by mass of the solvent was distilled off under reduced pressure to obtain a polymer (P1-4) solution.

  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 into the polymer (P1-4) solution obtained above, and under an air stream Stirring was started, and 29.9 parts by mass of 2-acryloyloxyethyl isocyanate was added dropwise over 1 hour while maintaining 60 ° C. 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, thereby confirming the disappearance of the isocyanate group by IR spectrum measurement, and adding 53.3 parts by mass of methyl isobutyl ketone. A methyl isobutyl ketone solution containing 50% by mass of the fluorinated curable resin (4) was obtained. As a result of measuring the molecular weight of the obtained fluorine-containing curable resin (4) by GPC (polystyrene equivalent molecular weight), the number average molecular weight was 2,000 and the weight average molecular weight was 12,000. The fluorine-containing polymerizable resin (2) has a fluorine content of 11% by mass and a polymerizable unsaturated group equivalent of 470 g / eq. Met.

(Example 5)
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. Subsequently, 20 parts by mass of the compound (A-2-1) having a poly (perfluoroalkylene ether) chain obtained in Synthesis Example 1 and 3-hydroxy-1-adamantyl methacrylate (the above formula (B1-1-1)) A compound solution obtained by dissolving 48.3 parts by mass in 166 parts by mass of methyl isobutyl ketone and 10.2 parts by mass of t-butylperoxy-2-ethylhexanoate as a polymerization initiator. Three types of dropping solutions with the polymerization initiator solution dissolved in parts by mass were set in separate dropping devices, and dropped simultaneously over 2 hours while maintaining the inside of the flask at 105 ° C. After completion of dropping, the mixture was stirred at 105 ° C. for 5 hours, and then 270 parts by mass of the solvent was distilled off under reduced pressure to obtain a polymer (P1-5) solution.

  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 into the polymer (P1-5) solution obtained above, and under an air stream. Stirring was started, and 31.7 parts by mass of 2-methacryloyloxyethyl isocyanate was added dropwise over 1 hour while maintaining 60 ° C. 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 to confirm disappearance of the isocyanate group by IR spectrum measurement, and 70 parts by mass of methyl isobutyl ketone was added to add fluorine. A methyl isobutyl ketone solution containing 50% by mass of the polymerizable resin (5) was obtained. As a result of measuring the molecular weight of the obtained fluorine-containing polymerizable resin (5) by GPC (polystyrene equivalent molecular weight), it was found that the number average molecular weight was 1,500 and the weight average molecular weight was 4,100. The fluorine-containing polymerizable resin (1) has a fluorine content of 11% by mass, and the polymerizable unsaturated group equivalent is 500 g / eq. Met.

(Comparative Example 1)
A glass flask equipped with a stirrer, a thermometer, a condenser, and a dropping device was charged with 68.8 parts by mass of methyl isobutyl ketone as a solvent, and the temperature was raised to 105 ° C. while stirring in a nitrogen stream. Next, 40 parts by mass of the compound (A-2-1) having a poly (perfluoroalkylene ether) chain obtained in Synthesis Example 1 and 28.8 parts by mass of 2-hydroxyethyl methacrylate were added to 82.6 parts by mass of methyl isobutyl ketone. 3 drops of a monomer solution dissolved in 1 part and a polymerization initiator solution in which 10.3 parts by mass of t-butylperoxy-2-ethylhexanoate as a polymerization initiator was dissolved in 55.1 parts by mass of methyl isobutyl ketone The liquids were set in separate dropping devices, and dropped simultaneously over 2 hours while maintaining the inside of the flask at 105 ° C. After completion of the dropping, the mixture was stirred at 105 ° C. for 5 hours, and then 169.3 parts by mass of the solvent was distilled off under reduced pressure to obtain a polymer (P ′) solution.

  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 into the polymer (P ′) solution obtained above and stirred under an air stream. Then, 31.2 parts by mass of 2-acryloyloxyethyl isocyanate was added dropwise over 1 hour while maintaining 60 ° C. 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 to confirm the disappearance of the isocyanate group by IR spectrum measurement, and 54.6 parts by mass of methyl isobutyl ketone was added. A methyl isobutyl ketone solution containing 50% by mass of the fluorine-containing polymerizable resin (6) was obtained. As a result of measuring the molecular weight of the obtained fluorine-containing polymerizable 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-containing polymerizable resin (6) has a fluorine content of 22% by mass, and the radical polymerizable unsaturated group equivalent is 456 g / eq. Met.

  Regarding the fluorine-containing polymerizable resins (1) to (6) obtained in Examples 1 to 5 and Comparative Example 1, the characteristic values such as molecular weight are summarized in Table 1.

(Example 6)
[Preparation of base resin composition of active energy ray-curable 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 (manufactured by BASF Japan Ltd.) as a photopolymerization initiator "Irgacure 184") 5 parts by mass, 54 parts by mass of toluene as a solvent, 28 parts by mass of 2-propanol, 28 parts by mass of ethyl acetate, and 28 parts by mass of propylene glycol monomethyl ether are mixed and dissolved to obtain an active energy ray-curable composition The base resin composition was obtained.

[Preparation of active energy ray-curable composition and preparation of cured coating film]
To 268 parts by mass of the base resin composition obtained above, 2 parts by mass of a solution containing 50% by mass of the fluorine-containing curable resin (1) obtained in Example 1 as a fluorine-containing surfactant (1 part as the resin content) Part) was added and mixed uniformly to obtain an active energy ray-curable composition. Next, this active energy ray-curable 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 cured coating film was obtained by irradiating the dried coating film with ultraviolet rays using an ultraviolet curing device (in a nitrogen atmosphere, a high-pressure mercury lamp, an ultraviolet irradiation amount of ² kJ / m ² ).

[Evaluation of antifouling properties]
The antifouling property of the surface of the cured coating film obtained above was evaluated from the following contact angles of water and n-dodecane.

[Measurement of contact angle of water and n-dodecane]
About the cured coating film surface, the contact angle of water and n-dodecane was measured using the contact angle measuring apparatus (Kyowa Interface Science Co., Ltd. "MODEL CA-W150").

[Evaluation of antifouling properties after wear treatment]
As an evaluation of antifouling durability, the contact angle of water and n-dodecane was measured in the same manner as described above for the cured coating film surface subjected to abrasion treatment. The wear treatment was performed by attaching a non-woven fabric (“Bencot S” manufactured by Asahi Kasei Fibers Co., Ltd.) to a jig using a reciprocating wear tester (“HEIDON Tribogear TYPE: 30S” manufactured by Shinto Kagaku Co., Ltd.) of 1.72N. It was performed by carrying out 5000 round-trip wear with a load of / cm ² .

[Strong alkali treatment of cured coatings]
The cured coating film obtained above was immersed in a 2.0 mol / L potassium hydroxide aqueous solution heated to 70 ° C. for 1 minute, washed with water, dried at 100 ° C. for 3 minutes, and then subjected to a strong alkali treatment. .

[Evaluation of scratch resistance]
Tribogear HEIDON reciprocating wear tester TYPE: 30S (made by Shinto Kagaku Co., Ltd.), wear tester (500g / The test was performed with 30 reciprocating wear at a load of cm ² . The number of scratches on the coating surface after the test was counted, and the scratch resistance was evaluated according to the following criteria.
A: The number of scratches is less than 5.
B: The number of scratches is less than 10.
C: The number of scratches is 10 or more and less than 50.
D: The number of scratches is 50 or more.

(Examples 7 to 10)
The same as Example 6 except that the fluorine-containing curable resins (2) to (5) obtained in Examples 2 to 5 were used instead of the fluorine-containing curable resin (1) used in Example 6, respectively. The active energy ray-curable composition was prepared, the cured coating film was prepared, the antifouling property was evaluated, and the scratch resistance was evaluated.

(Comparative Example 2)
In place of the fluorine-containing curable resin (1) used in Example 6, the same operation as in Example 6 was carried out except that the fluorine-containing curable resin (6) obtained in Comparative Example 1 was used. Preparation of a wire curable composition, preparation of a cured coating film, evaluation of antifouling properties and evaluation of scratch resistance were performed.

(Comparative Example 3)
The same procedure as in Example 6 was carried out without adding anything to the base resin composition of the active energy ray-curable composition prepared in Example 6 to produce a cured coating film, evaluation of antifouling properties, and scratch resistance. Sexuality was evaluated.

  The measurement and evaluation results are shown in Table 2.

  Curing coating of the active energy ray-curable compositions of Examples 6 to 10 to which the fluorine-containing polymerizable resins (1) to (5) obtained in Examples 1 and 2 which are the fluorine-containing polymerizable resins of the present invention were added. The membrane was found to have a high contact angle of water and n-dodecane and excellent antifouling properties. Moreover, it turned out that the contact angle of water and n-dodecane does not fall significantly even after abrasion treatment, and the antifouling durability is high. Furthermore, it has been found that it has excellent scratch resistance.

  On the other hand, Comparative Example 2 using the fluorine-containing polymerizable resin (6) having no adamantyl group produced in Comparative Example 1 has a high contact angle with water and n-dodecane and has excellent antifouling properties. However, it was found that the contact angle between water and n-dodecane after the abrasion treatment was greatly reduced, and the antifouling durability was not sufficient. Also, the scratch resistance was insufficient.

  In Comparative Example 3 in which no additive was added, it was found that the contact angle of water and n-dodecane was low, and the antifouling property was insufficient. Also, the scratch resistance was insufficient.

The bonding position of Y and the organic group having the reactive functional group (b1) represented by -XL in the general formula (B1-1) is bonded to any carbon atom in the adamantane structure. Moreover, you may have 2 or more about -XL. Furthermore, part or all of the hydrogen atoms bonded to the carbon atoms constituting the adamantane structure may be substituted with fluorine atoms, alkyl groups, or the like. Although X and Y in the general formula (B1-1) is an divalent organic group or a single bond, as the divalent organic group include a methylene group, propylene alkylene group, carbon atoms such as isopropylidene group An alkylene group having 1 to 8 atoms is exemplified.

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. Part is more preferable, and 0.3 to 7 parts by mass is further preferable.

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 into the polymer (P1-3) solution obtained above, and under an air stream Stirring was started, and 33.7 parts by mass of 2-acryloyloxyethyl isocyanate was added dropwise over 1 hour while maintaining 60 ° C. 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 to confirm the disappearance of the isocyanate group by IR spectrum measurement, and 56.3 parts by mass of methyl isobutyl ketone was added. A methyl isobutyl ketone solution containing 50% by mass of the fluorinated curable resin (3) was obtained. As a result of measuring the molecular weight of the obtained fluorinated curable resin (3) by GPC (polystyrene equivalent molecular weight), it was a number average molecular weight 1,700 and a weight average molecular weight 5,000. The fluorine-containing polymerizable resin ( 3 ) has a fluorine content of 5.6% by mass, and the polymerizable unsaturated group equivalent is 420 g / eq. Met.

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 into the polymer (P1-4) solution obtained above, and under an air stream Stirring was started, and 29.9 parts by mass of 2-acryloyloxyethyl isocyanate was added dropwise over 1 hour while maintaining 60 ° C. 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, thereby confirming the disappearance of the isocyanate group by IR spectrum measurement, and adding 53.3 parts by mass of methyl isobutyl ketone. A methyl isobutyl ketone solution containing 50% by mass of the fluorinated curable resin (4) was obtained. As a result of measuring the molecular weight of the obtained fluorine-containing curable resin (4) by GPC (polystyrene equivalent molecular weight), the number average molecular weight was 2,000 and the weight average molecular weight was 12,000. The fluorine-containing polymerizable resin ( 4 ) has a fluorine content of 11% by mass and a polymerizable unsaturated group equivalent of 470 g / eq. Met.

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 into the polymer (P1-5) solution obtained above, and under an air stream. Stirring was started, and 31.7 parts by mass of 2-methacryloyloxyethyl isocyanate was added dropwise over 1 hour while maintaining 60 ° C. 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 to confirm disappearance of the isocyanate group by IR spectrum measurement, and 70 parts by mass of methyl isobutyl ketone was added to add fluorine. A methyl isobutyl ketone solution containing 50% by mass of the polymerizable resin (5) was obtained. As a result of measuring the molecular weight of the obtained fluorine-containing polymerizable resin (5) by GPC (polystyrene equivalent molecular weight), it was found that the number average molecular weight was 1,500 and the weight average molecular weight was 4,100. The fluorine-containing polymerizable resin ( 5 ) has a fluorine content of 11% by mass, and the polymerizable unsaturated group equivalent is 500 g / eq. Met.

Claims (7)

  A polymer obtained by polymerizing a polymerizable unsaturated monomer, wherein the polymer has a poly (perfluoroalkylene ether) chain, an adamantyl group and a polymerizable unsaturated group in the structure of the polymer. A fluorine-containing polymerizable resin characterized by the above.   A poly (perfluoroalkylene ether) chain, a compound (A) having a polymerizable unsaturated group at both ends thereof, a polymerizable unsaturated monomer (B1) having an adamantyl group having a reactive functional group (b1), A compound (C) having a polymerizable unsaturated group and a functional group (c) having a reactivity with the functional group (b1) to a polymer (P1) obtained by copolymerizing as an essential monomer component The fluorine-containing polymerizable resin according to claim 1, which is obtained by reacting   A poly (perfluoroalkylene ether) chain, a compound (A) having a polymerizable unsaturated group at both ends thereof, and a polymerizable unsaturated monomer (B1) having an adamantyl group having a reactive functional group (b1) or A polymerizable unsaturated monomer (B2) having an adamantyl group having no reactive functional group (b1) and a polymerizable unsaturated monomer (B3) having a reactive functional group (b3) The polymer (P2) obtained by copolymerization as a monomer component has a functional group (c) having a reactivity with the functional group (b1) or the functional group (b3) and a polymerizable unsaturated group. The fluorine-containing polymerizable resin according to claim 1, obtained by reacting one or more compounds (C).   The reactive functional group (b1) or (b3) of the monomer (B1) or (B2) is selected from the group consisting of a hydroxyl group, an isocyanate group, an epoxy group, a carboxyl group, a carboxylic acid halide group, and an acid anhydride group. At least one functional group selected, the functional group (c) of the compound (C) is reactive with the reactive functional group (b1) or (b3), and is a hydroxyl group, an isocyanate group, or an epoxy. The fluorine-containing polymerizable resin according to claim 2 or 3, which is at least one functional group selected from the group consisting of a group, a carboxyl group, a carboxylic acid halide group and an acid anhydride group.   An activity comprising the fluorine-containing polymerizable resin according to any one of claims 1 to 4, and the active energy ray-curable resin (D) or the active energy ray-curable monomer (E). Energy ray curable composition.   The fluorine-containing polymerizable resin according to any one of claims 1 to 4 or the active energy ray-curable composition according to claim 5 is applied to a substrate and cured by irradiation with active energy rays. Cured product characterized by   An article having a cured coating film of the fluorine-containing polymerizable resin according to any one of claims 1 to 4 or the active energy ray-curable composition according to claim 5.

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