KR101768929B1 - Fluorine-containing polymerizable resin, active energy ray-curable composition using the same and cured product thereof - Google Patents

Abstract

A polymer obtained by polymerizing a polymerizable unsaturated monomer, wherein the polymer is a polymer having a poly (perfluoroalkylene ether) chain, an adamantyl group and a polymerizable unsaturated group in the structure of the polymer, An active energy ray curable composition to which a fluoropolymerizable resin is added, a cured product thereof, and an article having the cured coating film are provided. Such a fluoropolymerizable resin can impart excellent antifouling properties and scratch resistance to the surface of a cured coating film and can be used as a fluorinated surfactant. In addition, the cured coating film of the active energy ray curable composition containing the fluoropolymerizable resin is capable of maintaining excellent antifouling property even when the surface of the cured coating film is worn out by repeatedly wiping the contamination adhering to the surface thereof .

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fluorinated polymerizable resin, an active energy ray curable composition using the same, and a cured product thereof.

The present invention relates to a fluorine-containing surfactant capable of imparting excellent antifouling, lyophobic and scratch resistance to the surface of a coating film, fluorine-containing surfactants used as a fluorine-containing surface modifier, To a polymerizable resin. The present invention also relates to an active energy ray curable composition using the fluoropolymerizable 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. A resin plate (acrylic (PMMA) sheet, polycarbonate (PC) sheet, PMMA / PC composite sheet) or glass having transparency is used as the front surface protection plate. Since the resin sheet has a thickness of 0.3 mm to 2 mm and is softer than glass and easily scratched due to scratching, a hard coat layer is provided on the surface thereof to impart scratch resistance.

As a method for improving the scratch resistance by providing the hard coat layer, there is known a method of forming a cured coat film on the surface of a substrate obtained by curing a hard coat material containing a polyfunctional monomer such as polyfunctional (meth) acrylate. However, the conventional cured coating film has a problem that contamination is noticeable when fingerprints, sebum, sweat, cosmetics or the like are adhered thereto, and screen display becomes difficult to see. Further, in order to make the screen display easy to see, it was not easy to remove the contamination.

Therefore, in order to prevent the adhesion of the contamination and to impart the antifouling property capable of easily removing the adhered contamination, a fluororesin surfactant or a fluororesin surface modifier (hereinafter, also referred to simply as "fluororesin surfactant" ) As an additive has been studied. Particularly, in order to maintain the antifouling property, a monoacrylate having a fluorinated alkyl group, which has a polymerizable group and is designed to be immobilized by a covalent bond in a cured coating film, is copolymerized with an acrylic monomer having an active hydrogen, and then an acrylic- There has been proposed a polymerizable fluorinated surfactant having an unsaturated group obtained by reacting a monomer (for example, see Patent Document 1). The polymerizable fluorinated surfactant has a polymerizable group, and when used as an additive to a hard coating material, the polymerizable fluorinated surfactant binds to the polymerizable component in the composition by a covalent bond and is immobilized on the coating film. However, there has been a problem that the antifouling property is lowered if the surface of the hard coating material of the hard coating material is repeatedly wiped and the surface of the coating film is worn out. Further, there is a problem that when the surface of the cured coating film is worn by steel wool or the like, it is easily scratched.

Further, a poly (perfluoroalkylene ether) chain having a (perfluoroalkylene ether) chain and having a di (meth) acryloyl group at both terminals thereof as a raw material, and a polymerization type A fluorinated surfactant has been proposed (see, for example, Patent Document 2). This polymerizable fluorinated surfactant also has a problem that the antifouling property after abrasion is significantly lowered as shown in Patent Document 1, and it is liable to be scratched when the surface of the cured coating film is worn by steel wool or the like.

Therefore, in order to wipe away the stain adhered repeatedly, a material having antifouling properties and having high scratch resistance even if the surface of the coating film is worn has been demanded.

Japanese Patent Application Laid-Open No. 2007-246696 International Publication WO2009 / 133770

A problem to be solved by the present invention is to provide a fluorine-containing polymerizable resin which 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. The present invention also relates to an active energy ray curable composition which imparts a cured coating film having excellent antifouling properties and excellent scratch resistance even when the surface of the cured coating film is worn out by repeatedly wiping off contamination adhering to the surface of the cured coating film after application and curing, And an article having the cured product and the cured coating film.

DISCLOSURE OF THE INVENTION 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 and a polymer having an active energy The present invention has been accomplished on the basis of the finding that a good antifouling property can be imparted to the surface of a cured coating film and an excellent antifouling property can be maintained even if the surface of the coating film is worn by repeatedly wiping the contamination adhering to the surface of the coating film .

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

The present invention also relates to a cured product obtained by applying the fluorine-containing polymerizable resin or the active energy ray-curable composition onto a substrate, and curing the composition by irradiating with an active energy ray, and a cured product of the fluorine- To an article having a cured coating film.

The fluorine-containing polymerizable resin of the present invention can be applied to a substrate alone to form a cured film, thereby imparting antifouling properties to the substrate surface. The active energy ray curable composition to which the fluorine-containing polymerizable resin is added as a fluorine-containing surfactant acts to minimize the surface free energy peculiar to fluorine atoms when applied to a substrate, The compound is segregated (segregated) on the surface of the coating film, and surface modification that gives antifouling property to only the surface of the coating film is possible. Further, since the fluorine-containing polymerizable resin can be polymerized with other curable components in the active energy ray-curable composition, the polymerizable fluorine-containing compound of the present invention is more firmly immobilized in the cured coating film, so that heat treatment, It is possible to suppress the volatilization and desorption of the polymerizable fluorine compound or its decomposition product on the surface of the cured coating film.

The cured coating film using the fluorine-containing polymerizable resin of the present invention has excellent antifouling properties on the surface thereof and can maintain excellent antifouling properties even if the surface of the cured coating film is repeatedly wiped with dirt adhering to the surface of the cured coating film repeatedly Therefore, it is extremely useful as a hard coat layer for a front protective plate provided on the outermost surface of a liquid crystal display.

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a chart of IR spectra of the fluoropolymerizable resin (1) obtained in Example 1. Fig.
2 is a chart of the ¹³ C-NMR spectrum of the fluoropolymerizable resin (1) obtained in Example 1. Fig.
3 is a chart of GPC of the fluoropolymerizable resin (1) obtained in Example 1. Fig.

The fluorinated polymerizable resin of the present invention is a polymer obtained by polymerizing a polymerizable unsaturated monomer and is a polymer having a poly (perfluoroalkylene ether) chain, an adamantyl group and a polymerizable unsaturated group in the structure of the polymer By weight of a fluoropolymerizable resin.

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

(Production Method 1)

(A) having a poly (perfluoroalkylene ether) chain and a polymerizable unsaturated group at both terminals thereof and a polymerizable unsaturated monomer (B1) having an adamantyl group having a reactive functional group (b1) as essential monomer components (C) having a reactive group to the functional group (b1) and a compound (C) having a polymerizable unsaturated group are reacted with the polymer (P1)

(Production method 2)

(A) having a poly (perfluoroalkylene ether) chain and a polymerizable unsaturated group at both terminals thereof, a polymerizable unsaturated monomer (B1) having an adamantyl group having a reactive functional group (b1) or a reactive functional group To a polymer (P2) obtained by copolymerizing 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) as essential monomer components, (c) having reactivity with the functional group (b3) and at least one compound (C) having a polymerizable unsaturated group.

Next, each raw material used in the production of the fluoropolymerizable resin of the present invention will be described.

(A) having a poly (perfluoroalkylene ether) chain and a polymerizable unsaturated group at both terminals thereof as raw materials for the fluorine-containing polymerizable resin of the present invention will be described in the above Production Methods 1 and 2. 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 either a single kind or a mixture of plural kinds, and concretely, those represented by the following structural formula (a1) may be mentioned.

(In the structural formula (a1), X is the following structural formulas (a1-1) to (a1-5), all X in the structural formula (a1) may have the same structure, And n may be an integer of 1 or more representing a repeating unit.

Among these, a perfluoromethylene structure represented by the structural formula (a1-1) and a perfluoromethylene structure represented by the structural formula (a1-2) are preferable in that a coating film excellent in antifouling property can be obtained, It is particularly preferable that the ethylene structure coexists. Here, the ratio of the perfluoromethylene structure represented by the structural formula (a1-1) to the perfluoroethylene structure represented by the structural formula (a1-2) is in the molar ratio [structure (a1-1) / Structure (a1-2)] is 1/10 to 10/1 in terms of antifouling property. 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 still more preferably in the range of 12 to 50.

The poly (perfluoroalkylene ether) chain is included in one poly (perfluoroalkylene ether) chain in that it has excellent antifouling property and activity and is easy to improve solubility in a non-fluorinated curable resin composition. Is preferably in the range of 18 to 200, and more preferably in the range of 25 to 150.

Examples of the compound before introducing the polymerizable unsaturated group at both ends of the starting material of the compound (A) include the following general formulas (a2-1) to (a2-6). In the following structural formulas, " -PFPE- " represents the above-mentioned 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, acrylic (meth) acrylate represented by the structural formula U-1 is preferable because it is excellent in the availability of the compound (A) itself or the ease of preparation thereof or the polymerizability with the polymerizable unsaturated monomers (B1) And the methacryloyloxy group represented by the formula U-2 is preferable. Further, since the chemical resistance is improved, the methacryloyloxy group represented by the formula U-2 and the styrylmethoxy group represented by the formula U-5 are preferable.

Among the above-mentioned compounds (A), those represented by the following structural formulas (A-1) to (A-13) include those having an acryloyloxy group and the like. In the following structural formulas, " -PFPE- " represents a poly (perfluoroalkylene ether) chain.

(A-1), (A-2), (A), (A) and (A) -5) and (A-6). Since the chemical resistance is improved, the structural formulas (A-2), (A-4), (A-12) and (A-13) are preferable.

In order to produce the compound (A), for example, (meth) acrylic acid chloride or chloromethylstyrene is subjected to a dehydrochlorination reaction with respect to a compound having one hydroxyl group at both terminals of the poly (perfluoroalkylene ether) chain (Meth) acryloyloxyethyl isocyanate, a method obtained by urethane reaction of 2- (meth) acryloyloxyethyl isocyanate, a method obtained by esterifying anhydride of itaconic acid, a method of obtaining poly (perfluoroalkyl Hydroxybutyl acrylate glycidyl ether esterification reaction, a method of obtaining glycidyl methacrylate by an esterification reaction, a method of obtaining a poly (Perfluoroalkylene ether) chain, it is preferable that 2-hydroxyethyl acrylamide is reacted with a compound having one isocyanate group at both ends of the chain The key may be a way. Among these methods, there are a method of obtaining by dehydrochlorination reaction of (meth) acrylic acid chloride or chloromethylstyrene with a compound having one hydroxyl group at both terminals of the poly (perfluoroalkylene ether) chain and a method of obtaining 2- (meth) A method of urethane-forming a monooxyethyl isocyanate is particularly preferred in view of easy synthesis.

In the present invention, the term "(meth) acrylate" refers to one or both of methacrylate and acrylate, and the term "(meth) acryloyl group" refers to one of methacryloyl group and acryloyl group, Refers to both of them, and "(meth) acrylic acid" refers to one or both of methacrylic acid and acrylic acid.

In the above Production Method 1, the monomer (B1) to be a raw material of the fluorine-containing polymerizable resin of the present invention will be described. 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 contained in 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 of the monomer (B1) is preferably a carbon-carbon unsaturated double bond having a radical polymerizable property, and more specifically, a vinyl group, a (meth) acryloyl group, a maleimide group and the like , And a (meth) acryloyl group is more preferable because polymerization is facilitated. These monomers (B1) may be used singly or two or more of the reactive functional groups (b1) and polymerizable unsaturated groups may be used in combination.

As the monomer (B1) having a (meth) acryloyl group as a polymerizable unsaturated group, for example, a compound represented by the following general formula (B1-1) can be mentioned.

(Wherein 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 the organic group having the reactive functional group (b1) represented by -XL in the general formula (B1-1) and Y may be bonded to any carbon atom in the adamantane structure, and -XL You may have more than one. The hydrogen atom bonded to the carbon atom constituting the adamantane structure may be partially or entirely substituted with a fluorine atom, an alkyl group, or the like. In the general formula (B1-1), X and Y are each a divalent organic group or a single bond. Examples of the divalent organic group include a methylene group, a propylene group, and an isopropylidene group having 1 to 8 carbon atoms Alkylene group.

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

In the production method 2, the monomer (B2) which is a raw material of the fluorine-containing polymerizable resin of the present invention will be described. 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 a radical polymerizable property, and more specifically, a vinyl group, a (meth) acryloyl group, a maleimide group, (Meth) acryloyl group is more preferable because it can be easily polymerized. These monomers (B2) may be used alone or in combination of two or more.

As the monomer (B2) having a (meth) acryloyl group as a polymerizable unsaturated group, for example, a compound represented by the following general formula (B2-1) can be mentioned.

(Wherein 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. The hydrogen atom bonded to the carbon atom constituting the adamantane structure in the general formula (B2-1) may be partly or wholly replaced with a fluorine atom, an alkyl group or the like.

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

In the above Production Method 2, the monomer (B3) which is a raw material of the fluorine-containing polymerizable resin of the present invention will be described. Examples of the reactive functional group (b3) contained in 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 a radical polymerizable property, and more specifically, a vinyl group, a (meth) acryloyl group, a maleimide group, (Meth) acryloyl group is more preferable because it can be easily polymerized.

Specific examples of the monomer (B3) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2- Acrylate, 4-hydroxybutyl (meth) acrylate, 1,4-cyclohexanedimethanol mono (meth) acrylate, N- (2- hydroxyethyl) (meth) acrylamide, glycerin mono (Meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2- (meth) acryloyloxyethyl- Unsaturated monomers having a hydroxyl group such as hydroxyethyl phthalate and lactone-modified (meth) acrylate having a hydroxyl group at the terminal; Isocyanates such as 2- (meth) acryloyloxyethyl isocyanate, 2- (2- (meth) acryloyloxyethoxy) ethyl isocyanate and 1,1-bis ( An unsaturated monomer having a group; Unsaturated monomers having an epoxy group such as glycidyl methacrylate and 4-hydroxybutyl acrylate glycidyl ether; Unsaturated monomers having a carboxyl group such as (meth) acrylic acid, 2- (meth) acryloyloxyethylsuccinic acid, 2- (meth) acryloyloxyethylphthalic acid, maleic acid or itaconic acid; And acid anhydrides having an unsaturated double bond such as maleic anhydride and itaconic anhydride. These monomers (B3) may be used singly or in combination of two or more.

In producing the polymer (P1) or (P2) which is an intermediate of the fluorine-containing polymerizable resin of the present invention, the compound (A), the monomer (B1), the monomer ) And the monomer (B3), other polymerizable unsaturated monomer (B4) copolymerizable therewith may be used. Examples of the other polymerizable unsaturated monomer (B4) include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n- butyl (meth) (Meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, n-heptyl (Meth) acrylate having a polyoxyalkylene chain such as (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (Meth) acrylic acid esters; Aromatic vinyls such as styrene,? -Methylstyrene, p-methylstyrene and p-methoxystyrene; Maleimides such as maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide and cyclohexylmaleimide And the like.

In the above Production Method 1 or 2, the compound (C) as a raw material of the fluorine-containing polymerizable resin of the present invention will be described. Examples of the functional group (c) in the compound (C) 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) of the monomer (B1) or (B3) is a hydroxyl group, an isocyanate group, a carboxyl group, a carboxylic acid halide group or an epoxy group may be used as the functional group (c) (B) or (b3) is an isocyanate group, the functional group (c) may be a hydroxyl group. When the reactive functional group (b1) or (b3) is an epoxy group, a carboxyl group or a hydroxyl group may be used as the functional group When the reactive functional group (b1) or (b3) is a carboxyl group, the functional group (c) may include an epoxy group and a hydroxyl group.

Herein, in the case where the monomer (B1) and the monomer (B3) are used together in the production method 2, the reactive functional group (b1) and the reactive functional group (b3) When the reactive functional groups (b1) and (b3) react with a common functional group, one kind of compound (C) having a functional group (c) capable of reacting with the reactive functional groups (b1) and have. When the reactive functional group (b1) and the reactive functional group (b3) do not react with the common functional group, the compound (C) having the functional group (c) having reactivity with the reactive functional group (b1) And a compound (C) having a functional group (c) having reactivity are preferably used.

The polymerizable unsaturated group of the compound (C) is preferably a carbon-carbon unsaturated double bond having a radical polymerizable property, and more specifically, a vinyl group, a (meth) acryloyl group, a maleimide group and the like , And a (meth) acryloyl group is more preferable in view of good curability in an active energy ray-curable resin composition to be described later.

Specific examples of the compound (C) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) Acrylate, 4-hydroxybutyl (meth) acrylate, 1,4-cyclohexanedimethanol mono (meth) acrylate, N- (2- hydroxyethyl) (meth) acrylamide, glycerin mono (Meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2- (meth) acryloyloxyethyl- Unsaturated monomers having a hydroxyl group such as hydroxyethyl phthalate and lactone-modified (meth) acrylate having a hydroxyl group at the terminal; Isocyanates such as 2- (meth) acryloyloxyethyl isocyanate, 2- (2- (meth) acryloyloxyethoxy) ethyl isocyanate and 1,1-bis ( An unsaturated monomer having a group; Unsaturated monomers having an epoxy group such as glycidyl methacrylate and 4-hydroxybutyl acrylate glycidyl ether; Unsaturated monomers having a carboxyl group such as (meth) acrylic acid, 2- (meth) acryloyloxyethylsuccinic acid, 2- (meth) acryloyloxyethylphthalic acid, maleic acid or itaconic acid; And acid anhydrides having an unsaturated double bond such as maleic anhydride and itaconic anhydride. Further, 2-hydroxy-3-acryloyloxypropyl methacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, or the like having a plurality of polymerizable unsaturated groups may be used. These compounds (C) may be used singly or in combination of two or more.

Among the specific examples of the compound (C), from the viewpoint of favorable polymerization curability in ultraviolet irradiation, it is preferable to use 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 2- Acrylate, 4-hydroxybutyl acrylate, 1,4-cyclohexanedimethanol monoacrylate, N- (2-hydroxyethyl) acrylamide, 2-acryloyloxyethyl isocyanate, 1,1-bis Acryloyloxymethyl) ethyl isocyanate 4-hydroxybutyl acrylate glycidyl ether, and acrylic acid are preferable.

Next, a more specific production method of the fluorinated polymerizable resin of the present invention will be described using the raw materials exemplified above.

The method for producing the polymer (P1) or (P2) which is an intermediate of the fluorine-containing polymerizable resin of the present invention in the above production method 1 or 2 is characterized in that in the case of the production method 1, (A), the monomer (B1), the monomer (B2), and the monomer (B3) in the case of Production Method 2, and the other polymerizable unsaturated monomer (B4) And, if necessary, further polymerizing other polymerizable unsaturated monomer (B4) in an organic solvent using a polymerization initiator. The organic solvent used here is preferably ketones, esters, amides, sulfoxides, ethers or hydrocarbons. Specific examples thereof include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, Propyleneglycol monomethyl ether acetate, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, toluene, . These are suitably 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. If necessary, a chain transfer agent such as lauryl mercaptan, 2-mercaptoethanol, thioglycerol, ethyl thioglycolic acid or octyl thioglycolic acid may be used.

In Production Method 1 or 2, the polymer (P1) or (P2) obtained as described above is mixed with the functional group (c) having reactivity with the functional group (b1) or (b3) and the compound having a polymerizable unsaturated group ), The fluorinated polymerizable resin of the present invention is obtained.

The method of reacting the compound (C) with the polymer (P1) or (P2) may be carried out under the condition that the polymerizable unsaturated group of the compound (C) or the like does not polymerize. For example, 120 < [deg.] ≫ C. This reaction is preferably carried out in the presence of a catalyst or polymerization inhibitor, 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- 4-methylphenol and the like are used, and as the urethanization reaction catalyst, dibutyltin dilaurate, dibutyltin diacetate, tin octylate, zinc octylate or the like is used and the reaction temperature is 40 to 120 캜, Lt; 0 > C. When the functional group (b1) or (b3) is an epoxy group and the functional group (c) is a carboxyl group, or when the functional group (b1) or (b3) is a carboxyl group and the functional group (c) is an epoxy group Methoxyphenol, hydroquinone, 2,6-di-t-butyl-4-methylphenol or the like as the polymerization inhibitor, tertiary amines such as triethylamine as the esterification reaction catalyst, tetramethyl Tertiary phosphines such as triphenylphosphine and the like, quaternary phosphoniums such as tetrabutylphosphonium chloride, and the like are used, and the reaction temperature is 80 to 130 占 폚, particularly 100 to 120 占 폚 Lt; 0 > C.

The organic solvent used in the reaction is preferably ketones, esters, amides, sulfoxides, ethers and hydrocarbons. Specific examples thereof include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, , Butyl acetate, propylene glycol monomethyl ether acetate, dimethyl formamide, dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, toluene, . These may be suitably selected in consideration of boiling point and compatibility.

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

Here, the number average molecular weight (Mn) and the weight average molecular weight (Mw) are values obtained by converting into polystyrene based on gel permeation chromatography (hereinafter abbreviated as "GPC") measurement. The measurement conditions of GPC are as follows.

[Conditions for measuring GPC]

Measuring apparatus: "HLC-8220GPC" manufactured by Tosoh Corporation,

Column: " HHR-H " (6.0 mm ID x 4 cm) manufactured by TOSOH CORPORATION,

+ "TSK-GEL GMHHR-N" (7.8 mm ID × 30 cm) manufactured by Tosoh Corporation,

+ "TSK-GEL GMHHR-N" (7.8 mm ID × 30 cm) manufactured by Tosoh Corporation,

+ "TSK-GEL GMHHR-N" (7.8 mm ID × 30 cm) manufactured by Tosoh Corporation,

+ "TSK-GEL GMHHR-N" (7.8 mm ID × 30 cm) manufactured by Tosoh Corporation,

Detector: ELSD (Ortech's "ELSD2000")

Data processing: "GPC-8020 Model II Data Analysis Version 4.30" manufactured by Tosoh Corporation

Measurement conditions: Column temperature 40 캜

The developing solvent tetrahydrofuran (THF)

Flow rate 1.0 ml / min

Sample: A tetrahydrofuran solution of 1.0% by mass in terms of resin solid matter was filtered with a microfilter (5 μl).

Standard samples: 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".

(Monodisperse polystyrene)

Quot; A-500 " manufactured by Tosoh Corporation

&Quot; A-1000 " manufactured by Tosoh Corporation

Quot; A-2500 " manufactured by Tosoh Corporation

Quot; A-5000 " manufactured by Tosoh Corporation

Quot; F-1 " manufactured by Tosoh Corporation

Quot; F-2 " manufactured by Tosoh Corporation

Quot; F-4 " manufactured by Tosoh Corporation

Quot; F-10 " manufactured by Tosoh Corporation

Quot; F-20 " manufactured by Tosoh Corporation

Quot; F-40 " manufactured by Tosoh Corporation

Quot; F-80 " manufactured by Tosoh Corporation

Quot; F-128 " manufactured by Tosoh Corporation

Quot; F-288 " manufactured by Tosoh Corporation

Quot; F-550 " manufactured by Tosoh Corporation

The fluorine content in the fluorine-containing polymerizable resin of the present invention is preferably in the range of 1 to 50 mass%, more preferably in the range of 5 to 35 mass%, and more preferably in the range of 5 to 35 mass%, since both the antifouling property and the compatibility with other components can be achieved. , And more preferably in the range of 10 to 25 mass%. 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.

The polymerizable unsaturated group equivalent in the fluoropolymerizable resin of the present invention is excellent in scratch resistance of the cured coating film and is therefore preferably in the range of 200 to 3,500 g / eq., More preferably in the range of 250 to 2,000 g / eq. More preferably in the range of 300 to 1,500 g / eq., And particularly preferably in the range of 400 to 1,000 g / eq.

The fluorine-containing polymerizable resin of the present invention can be used as a main agent of the active energy ray curable composition, but since it has an extremely excellent surface modifying ability, the fluorine-containing surfactant , It is possible to impart excellent antifouling properties to the cured coating film.

The active energy ray-curable composition of the present invention contains the fluorine-containing polymerizable resin of the present invention. The active energy ray-curable composition contains the active energy ray curable resin (D) or the active energy ray curable 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. The fluorine-containing polymerizable resin of the present invention is preferably used as a fluorine-based surfactant in the active energy ray-curable composition.

The active energy ray-curable resin (D) may be at least one selected from the group consisting of urethane (meth) acrylate resin, unsaturated polyester resin, epoxy (meth) acrylate resin, polyester (meth) acrylate resin, And a resin having a mid group. In the present invention, a urethane (meth) acrylate resin is particularly preferable in view 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 have.

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 There may be mentioned diisocyanates such as diisocyanate, isophorone diisocyanate, norbornadiisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated tetramethyl xylylene diisocyanate, cyclohexyl diisocyanate And the like, Examples of the aromatic polyisocyanate compound include tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, 1,5-naphthalene diisocyanate, tolylidine diisocyanate and p-phenylenediisocyanate .

Examples of the acrylate compound having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl Hexanediol mono (meth) acrylate, neopentyl glycol mono (meth) acrylate, hydroxypivalic neopentyl (meth) acrylate, Mono (meth) acrylates of divalent alcohols such as glycol mono (meth) acrylate; Acrylate, trimethylolpropane di (meth) acrylate, ethoxylated trimethylolpropane (meth) acrylate, propoxylated trimethylolpropane di (meth) acrylate, glycerin di Mono or di (meth) acrylates of trihydric alcohols such as ethyl (meth) acrylate, di (meth) acryloyloxyethyl isocyanurate and mono or di (meth) acrylates having a hydroxyl group obtained by modifying a part of these alcoholic hydroxyl groups with epsilon -caprolactone Methacrylate; (Meth) acryloyl group having three or more functional groups such as pentaerythritol tri (meth) acrylate, ditrimethylol propane tri (meth) acrylate, dipentaerythritol penta , Or a polyfunctional (meth) acrylate having a hydroxyl group in which the compound is also modified with? -Caprolactone; (Meth) acrylate having an oxyalkylene chain such as dipropylene glycol mono (meth) acrylate, diethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and polyethylene glycol mono compound; (Meth) acrylate compounds having an oxyalkylene chain having a block structure such as polyethylene glycol-polypropylene glycol mono (meth) acrylate and polyoxybutylene-polyoxypropylene mono (meth) acrylate; A (meth) acrylate compound having a random oxyalkylene chain such as poly (ethylene glycol-tetramethylene glycol) mono (meth) acrylate and poly (propylene glycol-tetramethylene glycol) mono .

The reaction of the above aliphatic polyisocyanate compound or aromatic polyisocyanate compound with an acrylate compound having a hydroxyl group can be carried out by a conventional method in the presence of a urethanation catalyst. Specific examples of the urethanization catalyst usable herein include amines such as pyridine, pyrrole, triethylamine, diethylamine and dibutylamine, hopsphenols such as triphenylphosphine and triethylphosphine, dibutyltin di Organotin compounds such as laurate, octyltin triallate, octyltin diacetate, dibutyltin diacetate and tin octylate, and organometallic compounds such as zinc octylate.

Among these urethane acrylate resins, particularly preferred are those obtained by reacting an aliphatic polyisocyanate compound and a (meth) acrylate compound having a hydroxyl group, in view of excellent transparency of the cured coating film, good sensitivity to active energy rays and excellent curability Do.

Next, the unsaturated polyester resin is a curable resin obtained by polycondensation of an?,? - unsaturated dibasic acid or an acid anhydride thereof, an aromatic saturated dibasic acid or an acid anhydride thereof, and glycols and is a?,? - unsaturated dibasic Examples of the acid or its acid anhydride include maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, chloromaleic acid, and esters thereof. Examples of the aromatic saturated dibasic acids or acid anhydrides thereof include phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, nitrophthalic acid, tetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, halogenated anhydride and esters thereof. Examples of the aliphatic or alicyclic saturated dibasic acids include oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, glutaric acid, hexahydrophthalic anhydride and esters thereof. Examples of glycols include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, 2-methylpropane-1,3-diol, neopentyl glycol, triethylene glycol, tetra Ethylene glycol, 1,5-pentanediol, 1,6-hexanediol, bisphenol A, hydrogenated bisphenol A, ethylene glycol carbonate and 2,2-di- (4-hydroxypropoxydiphenyl) propane , And oxides such as ethylene oxide and propylene oxide may also be used.

Next, examples of the epoxy vinyl ester resin include those obtained by reacting (meth) acrylic acid with an epoxy group of an epoxy resin such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolak type epoxy resin or cresol novolak type epoxy resin .

Examples of the resin having a maleimide group include a bifunctional maleimide urethane compound obtained by urethanizing N-hydroxyethyl maleimide and isophorone diisocyanate, a bifunctional maleimide urethane compound obtained by esterifying maleimide acetic acid and polytetramethylene glycol, An ester compound, a tetra-functional maleimide ester compound obtained by esterifying maleic anhydride with a tetraethylene oxide adduct of pentaerythritol, a polyfunctional maleimide ester compound obtained by esterifying maleimide acetic acid and a polyhydric alcohol compound, and the like have. These active energy ray-curable resins (F) may be used singly or in combination of two or more.

Examples of the active energy ray-curable monomer (E) include ethyleneglycol di (meth) acrylate, diethyleneglycol di (meth) acrylate, triethyleneglycol di (meth) acrylate, Propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate having a number average molecular weight of 150 to 1000 Butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, (Meth) acrylate, trimethylolpropane tri (meth) acrylate, hexane diol di (meth) acrylate, hydroxypivalic acid ester neopentyl glycol di (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, pentaerythritol tetra (meth) acrylate, trimethylol propane di (meth) acrylate, dipentaerythritol penta (Meth) acrylate, dicyclopentenyl (meth) acrylate, methyl (meth) acrylate, propyl (meth) acrylate, butyl Acrylate such as octyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate and isostearyl (Meth) acrylate, glycidyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 3-chloro- Allyl (meth) (Meth) acrylate, 2-butoxyethyl (meth) acrylate, 2- (diethylamino) ethyl (Meth) acrylate, methoxydiethyleneglycol (meth) acrylate, methoxydipropylene glycol (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, nonylphenoxypoly (Meth) acrylate, polyoxyethylene (meth) acrylate, polyoxyethylene (meth) acrylate, propylene glycol (meth) acrylate, phenoxyethyl (Meth) acrylate, propylene glycol (meth) acrylate, polyethylene glycol-polybutylene glycol (meth) acrylate, polystyrylethyl (Meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, isobornyl (meth) acrylate, methoxylated cyclodecatriene ) Acrylate; Maleimide, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-butylmaleimide, N-hexylmaleimide, N-octylmaleimide, N-dodecylmaleimide, Maleimide ethyl carbonate, N-ethyl maleate, N-ethyl maleate, maleimide, N-phenyl maleimide, N-cyclohexyl maleimide, Maleimides such as N-hexamethylene bismaleimide, polypropylene glycol-bis (3-maleimidepropyl) ether, bis (2-maleimideethyl) carbonate and 1,4-dimaleimide cyclohexane have.

Of these, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, pentaerythritol tetra (meth) acrylate (Meth) acrylate having three or more functional groups such as a carboxyl group and a carboxyl group. These active energy ray-curable monomers (E) may be used singly or in combination of two or more.

When the fluorine-containing polymerizable resin of the present invention is used as the fluorine-containing surfactant in the active energy ray-curable composition of the present invention, the amount of the active energy ray-curable resin (D) and the active energy ray- Is preferably in the range of 0.01 to 20 parts by mass, more preferably in the range of 0.1 to 15 parts by mass, and still more preferably in the range of 0.5 to 10 parts by mass. When the amount of the fluorine-containing polymerizable resin of the present invention is within this range, the leveling property, the water-repellent / oil-repellent property and the antifouling property can be made sufficient, and the hardness and transparency of the composition after curing can be sufficient. In addition, since the proportion of the fluorinated polymerizable resin of the present invention occupying 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 used as a coating film, By setting the amount of the fluorinated polymerizable resin to be low and setting the amount of the fluorinated polymerizable resin of the present invention to be high in the case of the thin film, the fluorinated polymerizable resin of the present invention can be uniformly present on the surface of the coated film, High scratch resistance can be expected.

The fluorine-containing polymerizable resin or active energy ray-curable composition of the present invention can be formed into a cured coating film by applying an active energy ray to the base material and then coating the base material. This active energy ray refers to ionizing radiation such as ultraviolet ray, electron ray,? Ray,? Ray and? Ray. When ultraviolet rays are irradiated as active energy rays to form a cured coating film, it is preferable to add a photopolymerization initiator (F) to the fluoropolymerizable resin or the active energy ray curable composition to improve the curability. Further, if necessary, a photosensitizer may be further added to improve the curability. On the other hand, in the case of using ionizing radiation such as electron beams, alpha rays, beta rays and gamma rays, it is possible to rapidly cure even without using a photopolymerization initiator or a photosensitizer, so that it is necessary to add a photopolymerization initiator (F) There is no.

Examples of the photopolymerization initiator (F) include an intramolecular-type open-type photopolymerization initiator and a hydrogen-drawing type photopolymerization initiator. Examples of the intramolecular isotactic photopolymerization initiator include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 1- (4- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl-phenylketone, 2-methyl Acetophenone compounds such as 2-morpholino (4-thiomethylphenyl) propan-1-one and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone; Benzoin such as benzoin, benzoin methyl ether, and benzoin isopropyl ether; Acylphosphine oxide-based compounds such as 2,4,6-trimethylbenzoindienylphenylphosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide; Benzyl, methylphenylglyoxyester and the like.

Examples of the hydrogen-withdrawing photopolymerization initiator include benzophenone, methyl-4-phenylbenzophenone o-benzoylbenzoate, 4,4'-dichlorobenzophenone, hydroxybenzophenone, 4-benzoyl- Benzophenone based compounds such as diphenyl sulfide, acrylated benzophenone, 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone and 3,3'-dimethyl- compound; Thioxanthone compounds such as 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone and 2,4-dichlorothioxanthone; Aminobenzophenone compounds such as Michler's ketone and 4,4'-diethylaminobenzophenone; Butyl-2-chloroacridone, 2-ethyl anthraquinone, 9,10-phenanthrenequinone, camphorquinone, and the like.

Among the above photopolymerization initiators (F), 1-hydroxycyclohexyl phenyl ketone and / or 1-hydroxycyclohexyl phenyl ketone are preferred because of their excellent compatibility with the active energy ray-curable resin (D) and the active energy ray curable monomer (E) Benzophenone is preferable, and 1-hydroxycyclohexyl phenyl ketone is particularly preferable. These photopolymerization initiators (F) may 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-toluene sulfo And sulfur compounds such as nitrate.

The amount of the photopolymerization initiator and the photosensitizer is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 15 parts by mass, and more preferably 0.3 to 7 parts by mass, relative to 100 parts by mass of the nonvolatile component in the active energy ray curable composition desirable.

The active energy ray-curable composition of the present invention can be used for adjusting the viscosity and the refractive index, adjusting the color tone of a coating film, and other coating properties For example, various organic solvents, acrylic resins, phenol resins, polyester resins, polystyrene resins, urethane resins, urea resins, melamine resins, alkyd resins, epoxy resins, poly Various kinds of organic or inorganic particles such as polytetrafluoroethylene (PTFE), polyethylene, polypropylene, carbon, titanium oxide, alumina, copper, and silica fine particles, , A polymerization initiator, a polymerization inhibitor, an antistatic agent, a defoaming agent, a viscosity adjuster, a light stabilizer, a weather stabilizer, a heat stabilizer, an antioxidant, A lubricant, a lubricant, a release agent, a compatibilizing agent, a conductivity adjusting agent, a pigment, a dye, a dispersing agent, a dispersion stabilizer, a silicone, a hydrocarbon surfactant and the like may be used in combination.

Among the above components, 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, it is easy to adjust the film thickness. Examples of the organic solvent usable herein 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; And ketones such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. These solvents may be used alone or in combination of two or more.

Here, the amount of the organic solvent to be used is preferably in the range of 0.5 to 50 times, based on the total mass of the curing component, on the mass basis, although it depends on the intended use and the intended thickness and viscosity.

Examples of the active energy ray for curing the active energy ray-curable composition of the present invention include ionizing radiation such as ultraviolet rays, electron beams, alpha rays, beta rays, and gamma rays as described above. As specific energy sources or curing apparatuses, Such as fluorescent lamps for ultraviolet rays, carbon arc, xenon lamps, high pressure mercury lamps for copying, medium pressure or high pressure mercury lamps, ultra high pressure mercury lamps, electrodeless lamps, metal halide lamps, natural light, etc., And the like.

Among these, ultraviolet rays are particularly preferable, and it is preferable to irradiate ultraviolet rays under an inert gas atmosphere such as nitrogen gas in order to avoid curing inhibition by oxygen or the like. If necessary, heat may be used in combination as an energy source and cured by ultraviolet rays, followed by heat treatment.

The coating method of the active energy ray-curable composition of the present invention may vary depending on the use, but may be applied to various coating materials such as gravure coater, roll coater, comma coater, knife coater, air knife coater, curtain coater, kiss coater, A coating method using a coater, dipping, a screen printing, a spray, an applicator, a bar coater, or a molding method using various dies.

The cured coating film of the fluorine-containing polymerizable resin of the present invention is coated and cured on the surface of the article in order to impart excellent antifouling properties (ink repellency, to glossiness, etc.) and scratch resistance to impart antifouling properties and activity to the article surface can do. Further, since the fluorinated polymerizable resin of the present invention can be imparted with leveling property to the porcelain by adding the fluorinated surfactant or the fluorine surface modifier to the porcelain (coating material), the active energy ray hardening composition Has high leveling property.

Examples of articles that can impart antifouling properties and activity to the surface of the fluorine-containing polymerizable resin or active energy ray-curable composition of the present invention include polarizing plate films of liquid crystal displays (LCDs) such as TAC films; Various display screens such as a plasma display (PDP) and an organic EL display; Touch panel; A case of an electronic terminal such as a cellular phone also has a screen; A transparent protective film for a color filter (hereinafter referred to as "CF") for a liquid crystal display; An organic insulating film for a liquid crystal TFT array; Inkjet ink for electronic circuit formation; Optical recording media such as CD, DVD, and Blu-ray disc; Transfer film for insert mold (IMD, IMF); Rubber rollers for office automation equipment such as copying machines and printers; A glass surface of a reading unit of an OA such as a copying machine or a scanner; An optical lens such as a camera, a video camera, and a spectacle; Watches of watches such as wrist watches, glasses; Windows of various vehicles such as automobiles and railway cars; Cover glass or film for solar cells; Various construction materials such as lacquer plates; Window pane of a house; Woodworking materials such as furniture, artificial / synthetic leather, various plastic molded articles such as cases of household appliances, and FRP bathtubs. Antifouling property and activity can be imparted to the surface of the article by applying the fluorine-containing polymerizable resin or the 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. It is also possible to impart antifouling property and activity to the surface of the article by adding the fluoropolymerizable resin of the present invention to various paints suitable for each article and applying and drying the same.

Further, the porcelain obtained by adding the fluorine-containing polymerizable resin of the present invention to the active energy ray-curable composition can improve the leveling property and impart antifouling property (ink repellency) and activity (scratch resistance) to the surface of the coating film have. Examples of such porcelain include a hard coating material of an LCD polarizing plate film such as a TAC film, an anti glare (AG) coating material or an anti-reflection (LR) coating material; Hard coating materials for various display screens such as plasma display (PDP) and organic EL display; Hard coating material for touch panels; A color resist, a printing ink, an ink jet ink or a coating material for forming RGB pixels used in a CF used in an image pickup device such as a liquid crystal display, an organic EL display, a CCD, and a CMOS; Black resist for black matrix of CF, printing ink, ink jet ink or coating; A resin composition for a pixel barrier, such as a plasma display (PDP) or an organic EL display; A case paint or hard coating material of an electronic terminal such as a mobile phone; Screen hard coating materials for electronic terminals such as mobile phones; A transparent protective coating for protecting CF surface; A coating for an organic insulating film of a liquid crystal TFT array; Inkjet ink for electronic circuit formation; Hard coating materials for optical recording media such as CD, DVD, and Blu-ray disc; Hard coat material for transfer film for insert mold (IMD, IMF); Coating materials for rubber rollers for OA equipment such as copiers and printers; Glass coating materials for reading parts of OA devices such as copiers and scanners; Coating materials for optical lenses such as cameras, video cameras, and glasses; Watches of watches such as wristwatches, coatings for glass; Coating materials for windows of various vehicles such as automobiles and railroad cars; A coating for a solar cell cover glass or a film of an antireflection film; Printing inks or paints for various building materials such as painted surfaces; Coating materials for windowpanes of houses; Wood-based paints such as furniture; Artificial and synthetic leather coating materials; Paints or coating materials for various plastic molded articles such as cases of household appliances; A FRP bath coating material or a coating material.

Examples of articles which can impart antifouling property and activity to the surface of the fluorine-polymerizable resin or active energy ray-curable composition of the present invention include a prism sheet or a diffusion sheet which is a backlight member of an LCD. Further, by adding the fluorine-containing polymerizable resin of the present invention to a coating material for a prism sheet or a diffusion sheet, it is possible to improve the leveling property of the coating material and to impart scratch resistance (scratch resistance) and antifouling property to the coating film of the coating material have.

Further, since the cured coating film of the fluoropolymerizable resin of the present invention has a low refractive index, it can also be used as a porcelain for low refractive index layer in an antireflection layer for preventing visible light such as a fluorescent lamp on various display surfaces such as LCD. Antifouling properties can also be imparted to the coating film surface while maintaining the low refractive index of the coating film by adding the fluorine-containing polymerizable resin of the present invention to the porcelain for the antireflection layer, particularly the porcelain for low refractive index layer in the antireflection layer.

Examples of other applications in which the fluorine-polymerizable resin or active energy ray-curable composition of the present invention can be used include optical fiber clad materials, waveguides, sealing materials for liquid crystal panels, various optical sealants, and optical adhesives.

Particularly, when the active energy ray-curable composition of the present invention is used as an anti-glare coating material in the coating material for a protective film of a polarizing plate for LCD, inorganic or organic materials such as silica fine particles, acrylic resin fine particles, and polystyrene resin fine particles, It is preferable to blend the organic 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 because the antifogging property is excellent.

When the fluorine-containing polymerizable resin or active energy ray-curable composition of the present invention is used for an anti-glare coating material for a protective film of a polarizing plate for LCD, the coating material is brought into contact with the surface- And the surface of the coating film is embossed to impart antistatic properties to the surface of the coating film. It is also possible to apply the present invention to a transfer method in which a surface of a coating film is mirror-finished by irradiating an active energy ray from the side opposite to the mold or film after contacting the mold or film having a mirror surface before curing the porcelain.

[Example]

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

[Conditions for measuring IR spectrum]

Device: "IRPrestige-21" manufactured by Shimazu Seisakusho Co., Ltd.

The resin obtained in the examples was measured by the KBr method.

[Conditions for measuring ¹³ C-NMR spectrum]

Apparatus: "AL-400" manufactured by Nippon Denshi Co., Ltd.

Solvent: acetone-d ₆

[Conditions for measuring GPC]

Measuring apparatus: "HLC-8220GPC" manufactured by Tosoh Corporation,

Column: " HHR-H " (6.0 mm ID x 4 cm) manufactured by TOSOH CORPORATION,

+ "TSK-GEL GMHHR-N" (7.8 mm ID × 30 cm) manufactured by Tosoh Corporation,

+ "TSK-GEL GMHHR-N" (7.8 mm ID × 30 cm) manufactured by Tosoh Corporation,

+ "TSK-GEL GMHHR-N" (7.8 mm ID × 30 cm) manufactured by Tosoh Corporation,

+ "TSK-GEL GMHHR-N" (7.8 mm ID × 30 cm) manufactured by Tosoh Corporation,

Detector: ELSD (Ortech's "ELSD2000")

Data processing: "GPC-8020 Model II Data Analysis Version 4.30" manufactured by Tosoh Corporation

Measurement conditions: Column temperature 40 캜

The developing solvent tetrahydrofuran (THF)

Flow rate 1.0 ml / min

Sample: A tetrahydrofuran solution of 1.0% by mass in terms of resin solid matter was filtered with a microfilter (5 μl).

Standard samples: 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".

(Monodisperse polystyrene)

Quot; A-500 " manufactured by Tosoh Corporation

&Quot; A-1000 " manufactured by Tosoh Corporation

Quot; A-2500 " manufactured by Tosoh Corporation

Quot; A-5000 " manufactured by Tosoh Corporation

Quot; F-1 " manufactured by Tosoh Corporation

Quot; F-2 " manufactured by Tosoh Corporation

Quot; F-4 " manufactured by Tosoh Corporation

Quot; F-10 " manufactured by Tosoh Corporation

Quot; F-20 " manufactured by Tosoh Corporation

Quot; F-40 " manufactured by Tosoh Corporation

Quot; F-80 " manufactured by Tosoh Corporation

Quot; F-128 " manufactured by Tosoh Corporation

Quot; F-288 " manufactured by Tosoh Corporation

Quot; F-550 " manufactured by Tosoh Corporation

(Synthesis Example 1)

In a glass flask equipped with a stirrer, a thermometer, a cooling tube and a dropping device, 20 parts by mass of a perfluoropolyether compound having hydroxyl groups at both terminals and represented by the following formula (a2-1-1) 10 parts by mass of ether, 0.006 parts by mass of p-methoxyphenol as a polymerization inhibitor and 3.3 parts by mass of triethylamine as a neutralizing agent were charged, stirring was started in an air stream, and methacrylic acid chloride 3.1 Mass part was added dropwise over 2 hours. After completion of the dropwise addition, the reaction mixture was stirred at 10 ° C for 1 hour, stirred at 30 ° C for 1 hour, elevated to 50 ° C and stirred for 10 hours, and disappearance of methacrylic chloride was confirmed by gas chromatography measurement . Subsequently, 70 parts by mass of diisopropyl ether was added as a solvent, and then 80 parts by mass of ion-exchanged water was mixed and stirred. After that, the mixture was washed three times by separating and removing the aqueous layer. Subsequently, 0.02 parts by mass of p-methoxyphenol was added as a polymerization inhibitor, and 8 parts by mass of magnesium sulfate as a dehydrating agent was added. The mixture was completely dehydrated by standing for one day, and then the dehydrating agent was filtered off.

(Wherein X is a perfluoromethylene group and a perfluoroethylene group, an average of 7 perfluoromethylene groups per molecule and an average of 8 perfluoroethylene groups, and the average number of fluorine atoms is 46 , And the number average molecular weight by GPC is 1,500)

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

(Wherein X is a perfluoromethylene group and a perfluoroethylene group, an average of 7 perfluoromethylene groups per molecule and an average of 8 perfluoroethylene groups, and the average number of fluorine atoms is 46 to be)

(Example 1)

100 parts by mass of methyl isobutyl ketone as a solvent was charged into a glass flask equipped with a stirrer, a thermometer, a cooling tube and a dropping device, and the mixture was heated to 105 DEG 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 20 parts by mass of 3-hydroxy-1-adamantyl methacrylate -1-1)) in 120 parts by mass of methyl isobutyl ketone and 10.5 parts by mass of t-butylperoxy-2-ethylhexanoate as a polymerization initiator were dissolved in 80 parts by mass of methyl isobutyl ketone And the solution of the polymerization initiator dissolved in the solution were separately set in a separate dripping device, and the solution was dropped into the flask at the same time while maintaining the inside of the flask at 105 DEG C over 2 hours. After completion of the dropwise addition, the mixture was stirred at 105 ° C for 5 hours, and then 262.1 parts of the solvent was distilled off under reduced pressure to obtain a polymer (P1-1) solution.

Then, 0.1 part by mass of p-methoxyphenol as a polymerization inhibitor and 0.03 part by mass of tin octylate as a urethanation catalyst were charged in the polymer (P1-1) solution obtained above, and stirring was started in an air stream, And 29.9 parts by mass of 2-acryloyloxyethyl isocyanate was added dropwise for one hour. After completion of the dropwise addition, the mixture was stirred at 60 占 폚 for 2 hours, then heated to 80 占 폚 and stirred for 10 hours to confirm disappearance of the isocyanate group by IR spectroscopy and 53.7 parts by mass of methyl isobutyl ketone was added. ) Was contained in an amount of 50% by mass. The molecular weight of the resulting fluoropolymerizable resin (1) was measured by GPC (molecular weight in terms of polystyrene). As a result, the number average molecular weight was 1,500 and the weight average molecular weight was 3,900. The fluorine-containing polymerizable resin (1) had a fluorine content of 11 mass% and a polymerizable unsaturated group equivalent of 476 g / eq. 1 shows the IR spectrum of the fluorine-curable resin (1), FIG. 2 shows the ¹³ C-NMR spectrum, and FIG. 3 shows the GPC chart.

(Example 2)

A glass flask equipped with a stirrer, a thermometer, a cooling tube and a dropping device was charged with 77.6 parts by mass of methyl isobutyl ketone as a solvent and heated to 105 DEG C while stirring under a nitrogen stream. Subsequently, 40 parts by mass of the compound (A-2-1) having the poly (perfluoroalkylene ether) chain obtained in Synthesis Example 1 and 37.6 parts by mass of 3-hydroxy-1-adamantyl methacrylate were dissolved in methyl isobutyl And a polymerization initiator solution dissolved in 139 parts by mass of butyl ketone and a polymerization initiator solution in which 11.7 parts by mass of t-butylperoxy-2-ethylhexanoate as a polymerization initiator was dissolved in 16.2 parts by mass of methyl isobutyl ketone, Was set in a separate dripping apparatus, and the inside of the flask was dropped at the same time while maintaining the inside of the flask at 105 DEG C over 2 hours. After completion of the dropwise addition, the mixture was stirred at 105 DEG 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.

Then, 0.1 part by mass of p-methoxyphenol as a polymerization inhibitor and 0.03 part by mass of tin octylate as a urethanation catalyst were charged into the polymer (P1-2) solution obtained above, and stirring was started in an air stream, And 22.3 parts by mass of 2-acryloyloxyethyl isocyanate was added dropwise for one hour. After completion of the dropwise addition, the mixture was stirred at 60 캜 for 2 hours, then heated to 80 캜 and stirred for 10 hours, and disappearance of isocyanate groups was confirmed by IR spectroscopy, and 48.7 parts by mass of methyl isobutyl ketone was added. Was obtained in an amount of 50% by mass. The molecular weight of the resulting fluorine-curable resin (2) was measured by GPC (molecular weight in terms of polystyrene). As a result, the number average molecular weight was 1,800 and the weight average molecular weight was 5,400. The fluorine-containing polymerizable resin (2) had a fluorine content of 22 mass% and a polymerizable unsaturated group equivalent of 640 g / eq.

(Example 3)

A glass flask equipped with a stirrer, a thermometer, a cooling tube and a dropping device was charged with 66.3 parts by mass of methyl isobutyl ketone as a solvent, and the temperature was raised to 105 DEG C while stirring under a nitrogen stream. Subsequently, 10 parts by mass of the compound (A-2-1) having the poly (perfluoroalkylene ether) chain obtained in Synthesis Example 1 and 56.3 parts by mass of 3-hydroxy-1-adamantyl methacrylate were dissolved in methyl isobutyl And a polymerization initiator solution dissolved in 122.6 parts by mass of butyl ketone and a polymerization initiator solution in which 9.9 parts by mass of t-butylperoxy-2-ethylhexanoate as a polymerization initiator was dissolved in 10 parts by mass of methyl isobutyl ketone, Was set in a separate dripping apparatus, and the inside of the flask was dropped at the same time while maintaining the inside of the flask at 105 DEG C over 2 hours. After completion of the dropwise addition, the mixture was stirred at 105 ° C for 5 hours, and 154.7 parts by mass of the solvent was distilled off under reduced pressure to obtain a polymer (P1-3) solution.

Then, 0.1 part by mass of p-methoxyphenol as a polymerization inhibitor and 0.03 part by mass of tin octylate as a urethanation catalyst were charged in the polymer (P1-3) obtained above, and stirring was started in an air stream, And 33.7 parts by mass of 2-acryloyloxyethyl isocyanate was added dropwise for one hour. After completion of the dropwise addition, the mixture was stirred at 60 ° C for 2 hours, then heated to 80 ° C and stirred for 10 hours, and disappearance of the isocyanate group was confirmed by IR spectroscopy. 56.3 parts by mass of methyl isobutyl ketone was added. Was obtained in an amount of 50% by mass. The molecular weight of the obtained fluorine-curing resin (3) was measured by GPC (molecular weight in terms of polystyrene). As a result, the number average molecular weight was 1,700 and the weight average molecular weight was 5,000. The fluorine-containing polymerizable resin (3) had a fluorine content of 5.6% by mass and a polymerizable unsaturated group equivalent of 420 g / eq.

(Example 4)

A glass flask equipped with a stirrer, a thermometer, a cooling tube and a dropping device was charged with 35 parts by mass of methyl isobutyl ketone as a solvent, and the temperature was raised to 105 DEG C while stirring in 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 50.1 parts by mass of 3-hydroxy-1-adamantyl methacrylate were dissolved in methyl isobutyl And a polymerization initiator solution in which 10.6 parts by mass of t-butylperoxy-2-ethylhexanoate as a polymerization initiator and methyl isobutyl ketone were dissolved in 84.6 parts by mass of butyl ketone, Was set in a separate dripping apparatus, and the inside of the flask was dropped at the same time while maintaining the inside of the flask at 105 DEG C over 2 hours. After completion of the dropwise addition, the mixture was stirred at 105 DEG C for 5 hours, and 83.5 parts by mass of the solvent was distilled off under reduced pressure to obtain a polymer (P1-4) solution.

Then, 0.1 part by mass of p-methoxyphenol as a polymerization inhibitor and 0.03 part by mass of tin octylate as a urethanation catalyst were charged in the polymer (P1-4) solution obtained above, and stirring was started in an air stream, And 29.9 parts by mass of 2-acryloyloxyethyl isocyanate was added dropwise for one hour. After completion of the dropwise addition, the mixture was stirred at 60 ° C for 2 hours, then heated to 80 ° C and stirred for 10 hours to confirm disappearance of isocyanate groups by IR spectroscopy, and 53.3 parts by mass of methyl isobutyl ketone was added. Was obtained in an amount of 50% by mass. The molecular weight of the resulting fluorine-curable resin (4) was measured by GPC (molecular weight in terms of polystyrene). As a result, the number average molecular weight was 2,000 and the weight average molecular weight was 12,000. The fluorine-containing polymerizable resin (4) had a fluorine content of 11 mass% and a polymerizable unsaturated group equivalent of 470 g / eq.

(Example 5)

100 parts by mass of methyl isobutyl ketone as a solvent was charged into a glass flask equipped with a stirrer, a thermometer, a cooling tube and a dropping device, and the mixture was heated to 105 DEG 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 20 parts by mass of 3-hydroxy-1-adamantyl methacrylate -1-1)) in 166 parts by mass of methyl isobutyl ketone and 10.2 parts by mass of t-butylperoxy-2-ethylhexanoate as a polymerization initiator were dissolved in 34 parts by mass of methyl isobutyl ketone And the solution of the polymerization initiator dissolved in the solution were separately set in a separate dripping device, and the solution was dropped into the flask at the same time while maintaining the inside of the flask at 105 DEG C over 2 hours. After completion of the dropwise addition, the mixture was stirred at 105 DEG 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.

Then, 0.1 part by mass of p-methoxyphenol as a polymerization inhibitor and 0.03 part by mass of tin octylate as a urethanation catalyst were charged in the polymer (P1-5) solution obtained above, and stirring was started in an air stream, And 31.7 parts by mass of 2-methacryloyloxyethyl isocyanate was added dropwise for one hour. After completion of the dropwise addition, the mixture was stirred at 60 占 폚 for 2 hours, then heated to 80 占 폚 and stirred for 10 hours to confirm disappearance of the isocyanate group by IR spectroscopy and 70 parts by mass of methyl isobutyl ketone was added. ) Was contained in an amount of 50% by mass. The molecular weight of the resulting fluoropolymerizable resin (5) was measured by GPC (molecular weight in terms of polystyrene). As a result, the number average molecular weight was 1,500 and the weight average molecular weight was 4,100. The fluorine-containing polymerizable resin (5) had a fluorine content of 11 mass% and a polymerizable unsaturated group equivalent of 500 g / eq.

(Comparative Example 1)

A glass flask equipped with a stirrer, a thermometer, a cooling tube, 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 DEG C while stirring under a nitrogen stream. Subsequently, 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 dissolved in 82.6 parts by mass of methyl isobutyl ketone And 10.3 parts by mass of t-butylperoxy-2-ethylhexanoate as a polymerization initiator and a polymerization initiator solution dissolved in 55.1 parts by mass of methyl isobutyl ketone were added to a separate dropwise addition device And the solution was added dropwise at the same time while maintaining the inside of the flask at 105 DEG C over 2 hours. After completion of the dropwise addition, the mixture was stirred at 105 DEG C for 5 hours, and 169.3 parts by mass of the solvent was distilled off under reduced pressure to obtain a polymer (P ') solution.

Then, 0.1 part by mass of p-methoxyphenol as a polymerization inhibitor and 0.03 part by mass of tin octylate as a urethanation catalyst were charged into the polymer (P ') solution obtained above, and stirring was started in an air stream, , 31.2 parts by mass of 2-acryloyloxyethyl isocyanate was added dropwise for one hour. After completion of the dropwise addition, the mixture was stirred at 60 ° C for 2 hours, then heated to 80 ° C and stirred for 10 hours to confirm disappearance of the isocyanate group by IR spectroscopy and 54.6 parts by mass of methyl isobutyl ketone was added. ) Was contained in an amount of 50% by mass. The molecular weight of the resulting fluoropolymerizable resin (6) was measured by GPC (molecular weight in terms of polystyrene). As a result, the number average molecular weight was 2,200 and the weight average molecular weight was 6,500. The fluorine-containing polymerizable resin (6) had a fluorine content of 22 mass% and a radical polymerizable unsaturated group equivalent of 456 g / eq.

The properties of the fluorine-containing polymerizable resins (1) to (6) obtained in Examples 1 to 5 and Comparative Example 1 are summarized in Table 1.

[Table 1]

(Example 6)

[Preparation of base resin composition of active energy ray curable composition]

125 parts by mass of an ultraviolet curing type urethane acrylate resin ("Unidick 17-806" manufactured by DIC Corporation; butyl acetate solution having a resin content of 80% by mass), 1-hydroxycyclohexyl phenyl ketone (BASF Japan Co., 5 parts by mass as a solvent, 54 parts by mass of toluene, 28 parts by mass of 2-propanol, 28 parts by mass of ethyl acetate and 28 parts by mass of propylene glycol monomethyl ether were mixed and dissolved to obtain an active energy ray- To obtain a base resin composition.

[Preparation of active energy ray curable composition and production of cured coating film]

To 268 parts by mass of the base resin composition obtained above, 2 parts by mass (1 part by mass as a resin component) of a 50% by mass solution of the fluorine-curing resin (1) obtained in Example 1 as a fluorine-containing surfactant was added and uniformly mixed To obtain an active energy ray curable composition. Subsequently, this active energy ray-curable composition was applied to a polyethylene terephthalate (PET) film having a thickness of 188 占 퐉 using Barcoater No. 13, and then put in a drier at 60 占 폚 for 5 minutes to volatilize the solvent. Next, the dried coating film was irradiated with ultraviolet rays using an ultraviolet curing apparatus (under a nitrogen atmosphere, a high-pressure mercury lamp, and an ultraviolet ray irradiation amount of ² kJ / m ² ) to obtain a cured coating film.

[Evaluation of antifouling property]

The antifouling property of the surface of the cured coating film obtained above was evaluated by the following contact angle of water and n-dodecane.

[Measurement of contact angle of water and n-dodecane]

The contact angle of water and n-dodecane was measured with respect to the surface of the cured coating film using a contact angle measuring apparatus (" MODELCA-W150 " manufactured by Kyowa Chemical Industry Co., Ltd.).

[Evaluation of antifouling property after abrasion treatment]

As an evaluation of the antifouling durability, the measurement of the contact angle of water and n-dodecane with respect to the surface of the cured coating film subjected to the abrasion was carried out as described above. The abrasion treatment was carried out using a nonwoven fabric (manufactured by Asahi Kasei Co., Ltd.) using a reciprocating abrasion tester ("HEIDON Tribogear TYPE 30S" manufactured by Shinto Kagaku K.K.) Quot; Bencoat S ") was attached and subjected to 5000 reciprocating abrasions at a load of 1.72 N / cm < ² >.

[Strong alkali treatment of hard coat]

The cured coating film obtained above was immersed in an aqueous solution of 2.0 mol / L potassium hydroxide heated at 70 캜 for 1 minute, washed with water and then dried at 100 캜 for 3 minutes to carry out a strong alkali treatment.

[Evaluation of scratch resistance]

(Manufactured by Nihon Steel Wool Co., Ltd.) to a circular jig having a diameter of 27 mm by using a tri-viewer HEIDON reciprocating abrasion tester TYPE: 30S (manufactured by Shinto Kagaku K.K.) 500 g / cm < ² > load). The number of scratches on the surface of the coated film after the test was counted, and scratch resistance was evaluated according to the following criteria.

A: Less than 5 scratches

B: Less than 10 scratches

C: The number of scratches is 10 or more and less than 50

D: More than 50 scratches

(Examples 7 to 10)

(2) to (5) obtained in Examples 2 to 5 were respectively used instead of the fluorine-curing resin (1) used in Example 6 to obtain an active energy ray curable resin Preparation of a composition, preparation of a cured coating film, evaluation of antifouling property and evaluation of scratch resistance were carried out.

(Comparative Example 2)

The procedure of Example 6 was repeated except that the fluorine-curing resin (6) obtained in Comparative Example 1 was used instead of the fluorine-curing resin (1) used in Example 6 to prepare an active energy ray- Evaluation of antifouling property and evaluation of scratch resistance.

(Comparative Example 3)

The base resin composition of the active energy ray curable composition prepared in Example 6 was operated in the same manner as in Example 6 without adding anything to prepare a cured coating film, evaluation of antifouling property and evaluation of scratch resistance.

The measurement and evaluation results are shown in Table 2.

[Table 2]

The curable coating films of the active energy ray-curable compositions of Examples 6 to 10 to which the fluorine-polymerizable resins (1) to (5) obtained in Examples 1 and 2, which are the fluorine-polymerizable resins of the present invention, - It was found that the contact angle of dodecane was high and it had excellent antifouling property. Also, it was found that the contact angle of water and n-dodecane did not significantly decrease even after the abrasion treatment, and that the antifouling persistence was also high. Further, it was also found to have excellent scratch resistance.

On the other hand, Comparative Example 2 using the fluorine-polymerizable resin (6) having no adamantyl group prepared in Comparative Example 1 had a high contact angle with water and n-dodecane and had excellent antifouling properties. However, And the contact angle of n-dodecane were greatly lowered, indicating that the durability persistence was not sufficient. In addition, 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. In addition, scratch resistance was insufficient.

Claims (7)

A polymer obtained by polymerizing a polymerizable unsaturated monomer, wherein the polymer is a fluoropolymerizable resin which is a polymer having a poly (perfluoroalkylene ether) chain, an adamantyl group and an active energy ray-curable polymerizable unsaturated group in the structure of the polymer,
(A) having a poly (perfluoroalkylene ether) chain and a polymerizable unsaturated group at both terminals thereof, and a polymerizable unsaturated monomer having an adamantyl group having a functional group (b1) (B1 (C) having a reactive group to the functional group (b1) and a compound (C) having a polymerizable unsaturated group to a polymer (P1) obtained by copolymerizing a polymerizable unsaturated group-
Wherein the functional group (b1) of the monomer (B1) is at least one functional group 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,
Wherein the functional group (c) of the compound (C) is at least one functional group 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 which is reactive with the functional group
Wherein the fluorinated polymerizable resin is a fluorinated polymer. A polymer obtained by polymerizing a polymerizable unsaturated monomer, wherein the polymer is a fluoropolymerizable resin which is a polymer having a poly (perfluoroalkylene ether) chain, an adamantyl group and an active energy ray-curable polymerizable unsaturated group in the structure of the polymer,
(A) having a poly (perfluoroalkylene ether) chain and a polymerizable unsaturated group at both terminals thereof, and a polymerizable unsaturated monomer having an adamantyl group having a functional group (b1) (B1 (P2) obtained by copolymerizing a polymerizable unsaturated monomer (B2) having an adamantyl group having no functional group (b1) or a polymerizable unsaturated monomer (B3) having a functional group (b3) as essential monomer components, , A functional group (c) having reactivity with the functional group (b1) or the functional group (b3) and at least one compound (C) having a polymerizable unsaturated group,
Wherein the functional group (b1) or the functional group (b3) of the monomer (B1) or the monomer (B3) is at least one functional group selected from the group consisting of hydroxyl group, isocyanate group, epoxy group, carboxyl group, carboxylic acid halide group and acid anhydride group,
Wherein the functional group (c) of the compound (C) is reactive with the functional group (b1) or the functional group (b3) and is selected from the group consisting of hydroxyl group, isocyanate group, epoxy group, carboxyl group, carboxylic acid halide group and acid anhydride group At least one functional group
Wherein the fluorinated polymerizable resin is a fluorinated polymer. An active energy ray curable composition comprising the fluorine-containing polymerizable resin according to any one of claims 1 to 3 and an active energy ray-curable resin (D) or an active energy ray-curable monomer (E). A cured product obtained by applying the fluorinated polymerizable resin according to any one of claims 1 to 3 onto a substrate and irradiating with an active energy ray to cure the fluorinated polymerizable resin. A cured product obtained by applying the active energy ray-curable composition according to claim 3 onto a base material and irradiating with an active energy ray to cure the active energy ray-curable composition. An article characterized by having a cured coating film of the fluorinated polymerizable resin according to any one of claims 1 to 3. An article comprising a cured coating film of the active energy ray-curable composition according to claim 3.

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