JP2013095776A - Fluorine-containing polymerizable resin, active-energy ray-curable composition including the same, and cured product obtained therefrom - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a fluorine-containing polymerizable resin capable of imparting excellent scratch resistance to a surface of a cured coating film formed of an active-energy ray-curable composition by adding the resin to the composition, the scratch resistance being such as not to be deteriorated even when the surface is processed with chemicals such as strong alkalis, and also to provide an active-energy ray-curable composition including the fluorine-containing polymerizable resin, a cured product obtained from the composition, and an article including a cured coating film formed of the composition.SOLUTION: The fluorine-containing polymerizable resin includes a polymer obtained by reacting a compound (D) with a polymer (P), the compound (D) having a polymerizable unsaturated group and a functional group (d) that has a reactivity to a reactive functional group (c), and the polymer (P) being obtained by polymerizing a compound (A) having a poly (perfluro alkylene ether) chain and a polymerizable unsaturated group at both ends of the chain, a polymerizable unsaturated monomer (B) having a silicone group, and a polymerizable unsaturated group (C) having the functional group (c), which are included as essential monomer components, at a specified ratio.

Description

  The present invention relates to a fluorine-containing polymerizable resin that can be added to an active energy ray-curable composition to impart excellent scratch resistance to the surface of a cured coating film of the composition. 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 a cured coating film of the composition.

  Conventionally, a hard coat made of an active energy ray-curable composition for preventing scratches on the outermost surface of a flat panel display screen such as a liquid crystal display (LCD), a plasma display (PDP), and an organic EL display (OELD). A hard coat layer is provided by applying and curing the material.

  As a method of improving the scratch resistance by providing the hard coat layer, a hard coat material containing a polyfunctional monomer such as polyfunctional (meth) acrylate was applied to the surface layer of the polarizing plate and cured. A method of providing a cured coating film is known. However, although this cured coating film can raise the surface hardness of the cured coating film to some extent, the scratch resistance is insufficient. Further, in applications where saponification treatment (strong alkali treatment) is used, such as a triacetyl cellulose (hereinafter abbreviated as “TAC”) film used for polarizing plates of liquid crystal displays, a cured coating film is obtained after saponification treatment. There was a problem that the scratch resistance of the surface was greatly reduced.

  On the other hand, a fluorine-containing polymerizable resin having a poly (perfluoroalkylene ether) chain and a polymerizable unsaturated group can be added to the active energy ray-curable composition to impart antifouling properties to the cured coating film surface. It has been proposed (see, for example, Patent Document 1). However, the cured coating film of the active energy ray-curable composition to which the fluorine-containing polymerizable resin is added has improved antifouling property and high antifouling property after saponification treatment. Later scratch resistance was insufficient.

  Further, a fluorine-containing polymerizable resin having a poly (perfluoroalkylene ether) chain, a silicone group and a polymerizable unsaturated group is added to the antireflection coating composition to impart antifouling properties to the antireflection film surface. It has been proposed. However, the cured coating film of the antireflective coating composition to which this fluorine-containing polymerizable resin was added also had a high antifouling property after saponification treatment, but under severer conditions after saponification treatment. There was a problem that the scratch resistance was not sufficient.

  Therefore, there has been a demand for a material capable of imparting excellent scratch resistance to the surface of a cured coating film that can prevent scratches even after saponification treatment (strong alkali treatment).

International Publication WO2009 / 133770 JP 2011-094009 A

  The problem to be solved by the present invention is that by adding to the active energy ray curable composition, it is possible to impart excellent scratch resistance to the cured coating film surface of the composition, An object of the present invention is to provide a fluorine-containing polymerizable resin capable of imparting excellent scratch resistance that does not decrease even when treated with a chemical such as a strong alkali. Another object is to provide an active energy ray-curable composition using the fluorine-containing polymerizable resin, a cured product thereof, and an article having a cured coating film of the composition.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have made a poly (perfluoroalkylene ether) chain, a compound (A) having a polymerizable unsaturated group at both ends thereof, and a polymerization having a silicone group. Polymer (P) obtained by copolymerizing polymerizable unsaturated monomer (B) and polymerizable unsaturated monomer (C) having a reactive functional group (c) as essential monomer components And a compound obtained by reacting a functional group (d) having a reactivity with the functional group (c) and a compound (D) having a polymerizable unsaturated group, wherein the compound (A) and Curing of an active energy ray-curable composition containing a fluorine-containing polymerizable resin comprising a polymer having a mass ratio [(A) / (B)] with the monomer (B) in a certain range. The coating surface was found to have excellent scratch resistance even after saponification treatment. It was completed.

That is, the present invention relates to a reaction between a poly (perfluoroalkylene ether) chain, a compound (A) having a polymerizable unsaturated group at both ends thereof, a polymerizable unsaturated monomer (B) having a silicone group, The polymer (P) obtained by copolymerizing a polymerizable unsaturated monomer (C) having a functional group (c) as an essential monomer component is reactive to the functional group (c). A fluorine-containing polymerizable resin comprising a polymer obtained by reacting a functional group (d) having a compound and a compound (D) having a polymerizable unsaturated group,
The mass ratio [(A) / (B)] of the compound (A) and the monomer (B) is in the range of 25/75 to 70/30,
The reactive functional group (c) is at least one reactive 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;
The functional group (d) is reactive to the functional group (c) and at least 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. The present invention relates to a fluorine-containing polymerizable resin characterized by being one functional group.

  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.

  When the fluorine-containing polymerizable resin of the present invention is added to the active energy ray-curable composition, the surface of the cured coating film is provided with a slip property and excellent scratch resistance is obtained. Moreover, since this scratch resistance can be exhibited even in a cured coating film that has been subjected to saponification treatment (strong alkali treatment), it is also useful as a material for a hard coat material of a TAC film used for a polarizing plate of a 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 comprises a poly (perfluoroalkylene ether) chain, a compound (A) having a polymerizable unsaturated group at both ends thereof, and a polymerizable unsaturated monomer (B) having a silicone group. And a polymer (P) obtained by copolymerizing a polymerizable unsaturated monomer (C) having a reactive functional group (c) as an essential monomer component, the functional group (c) A fluorine-containing polymerizable resin comprising a polymer obtained by reacting a functional group (d) having reactivity with a compound (D) having a polymerizable unsaturated group,
The mass ratio [(A) / (B)] of the compound (A) and the monomer (B) is in the range of 25/75 to 70/30,
The reactive functional group (c) is at least one reactive 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;
The functional group (d) is reactive to the functional group (c) and at least 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. It is a polymer obtained by reacting a fluorine-containing polymerizable resin characterized by being one functional group.

  Each raw material used for manufacture of said fluorine-containing polymerizable resin of this invention is demonstrated.

  The poly (perfluoroalkylene ether) chain, which is a raw material for the fluorine-containing polymerizable resin of the present invention, and the compound (A) having a polymerizable unsaturated group at both ends 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 preferable in terms of easy reaction in production.

  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.

  Next, the monomer (B) will be described. As a silicone group which the said monomer (B) has, what is represented by the following general formula (1) or (2) is mentioned, for example.

（式中、Ｒ、Ｒ’、Ｒ’’及びＲ’’’は、それぞれ独立に炭素原子数１〜１８のアルキル基又はフェニル基を表し、また、ｎは繰り返し単位数であり、１〜２００の整数を表す。）

(In the formula, R, R ′, R ″ and R ′ ″ each independently represents an alkyl group having 1 to 18 carbon atoms or a phenyl group, and n is the number of repeating units. Represents an integer.)

  Moreover, as a polymerizable unsaturated group which the said monomer (B) has, the carbon-carbon unsaturated double bond which has radical polymerizability is preferable, and a (meth) acryloyl group, a vinyl group, a maleimide group, etc. are mentioned. . Among these, (meth) acryloyl is easy because of the availability of raw materials, the ease of controlling the compatibility with each compounding component in the active energy ray-curable composition described later, or the good polymerization reactivity. Groups are preferred.

  Specific examples of the monomer (B) include monomers represented by the following general formulas (B1) to (B3). These monomers (B) can be used alone or in combination of two or more.

（式中、Ｒ^１は水素原子又はメチル基を表し、Ｒ^３〜Ｒ^６及びＲ^１０〜Ｒ^１２はそれぞれ独立に炭素原子数１〜１８のアルキル基又はフェニル基を表し、Ｒ^２及びＲ^７〜Ｒ^９はそれぞれ独立に炭素原子数１〜８のアルキル基又はフェニル基を表す。また、ｍは１〜６の整数を表し、ｎは０〜２００の整数を表し、ｒ、ｓ及びｔは、それぞれ独立に１〜２００の整数を表す。）

(In the formula, R ¹ represents a hydrogen atom or a methyl group, R ^{3 to} R ⁶ and R ^{10 to} R ¹² each independently represents an alkyl group having 1 to 18 carbon atoms or a phenyl group, and R ² and R ^7. ~ R ⁹ each independently represents an alkyl group or phenyl group having 1 to 8 carbon atoms, m represents an integer of 1 to 6, n represents an integer of 0 to 200, and r, s, and t represent And each independently represents an integer of 1 to 200.)

  The mass ratio [(A) / (B)] of the compound (A) and the monomer (B) is in the range of 10/90 to 85/15 because high scratch resistance is obtained. In order to obtain higher scratch resistance, the range of 15/85 to 80/20 is preferable, the range of 20/80 to 75/25 is more preferable, and the range of 25/75 to 70/30 is even more preferable.

  Next, the monomer (C) will be described. Examples of the reactive functional group (C) that the monomer (C) has 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 (C) 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 (C) 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 (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) Isocyanate group-containing unsaturated monomers such as ethyl isocyanate; Epoxy group-containing unsaturated monomers such as glycidyl methacrylate and 4-hydroxybutyl acrylate glycidyl ether; (meth) acrylic acid, 2- (meth) acryloyloxyethyl succinic acid Carboxyl group-containing unsaturated monomers such as 2- (meth) acryloyloxyethylphthalic acid, maleic acid and itaconic acid; acid anhydrides having an unsaturated double bond such as maleic anhydride and itaconic anhydride It is done. These monomers (C) can be used alone or in combination of two or more.

  Further, when producing the polymer (P) that is an intermediate of the fluorine-containing polymerizable resin of the present invention, in addition to the compound (A), the monomer (B), and the monomer (C), You may use the other polymerizable unsaturated monomer which can be copolymerized with these. Examples of such other polymerizable unsaturated monomers include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, 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) acrylate , Dodecyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, (meth) acrylates such as (meth) acrylate having a polyoxyalkylene chain; styrene, α-methylstyrene, p-methylstyrene , - aromatic vinyl such as methoxystyrene; maleimide, methyl maleimide, ethyl maleimide, propyl maleimide, butyl maleimide, hexyl maleimide, octyl maleimide, dodecyl maleimide, stearyl maleimide, phenyl maleimide, maleimide such as cyclohexyl maleimide.

  Next, the compound (D) will be described. Examples of the functional group (d) possessed by the compound (D) include a hydroxyl group, an isocyanate group, an epoxy group, a carboxyl group, a carboxylic acid halide group, and an acid anhydride group. When the reactive functional group (c) of the monomer (C) is a hydroxyl group, examples of the functional group (d) include an isocyanate group, a carboxyl group, a carboxylic acid halide group, and an epoxy group. When the group (c) is an isocyanate group, examples of the functional group (d) include a hydroxyl group. When the reactive functional group (c) is an epoxy group, the functional group (d) includes a carboxyl group and a hydroxyl group. In the case where the reactive functional group (c) is a carboxyl group, examples of the functional group (d) include an epoxy group and a hydroxyl group. These may be a combination of a plurality of functional groups. In addition, the polymerizable unsaturated group of the compound (D) 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 group is more preferable from the viewpoint of good curability in the active energy ray-curable composition described later.

  Specific examples of the compound (D) 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 Carboxyl group-containing unsaturated monomers such as succinic acid, 2- (meth) acryloyloxyethylphthalic acid, maleic acid and itaconic acid; acid anhydrides having unsaturated double bonds such as maleic anhydride and itaconic anhydride Is mentioned. 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 (D) can be used alone or in combination of two or more.

  Among the specific examples of the compound (D), 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.

  The method for producing the polymer (P) which is an intermediate of the fluorine-containing polymerizable resin of the present invention includes the compound (A), the monomer (B) and the monomer (C), and further if necessary. And a method of polymerizing other polymerizable unsaturated monomers in an organic solvent using a polymerization initiator. As the organic solvent used here, ketones, esters, amides, sulfoxides, ethers, hydrocarbons are preferable. Specifically, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, butyl acetate, Examples include propylene glycol monomethyl ether acetate, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, toluene, xylene and the like. These are appropriately selected in consideration of boiling point, compatibility, and polymerizability. Examples of the 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.

  By reacting the polymer (P) obtained as described above with the functional group (d) having a reactivity with the functional group (c) and the compound (D) having a polymerizable unsaturated group, The fluorine-containing polymerizable resin of the present invention is obtained.

  The method of reacting the compound (D) with the polymer (P) may be performed under the condition that the polymerizable unsaturated group of the compound (D) or the like does not polymerize. For example, the temperature condition is 30 to 120 ° C. It is preferable to adjust the reaction to the range. 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 (c) is a hydroxyl group and the functional group (d) is an isocyanate group, p-methoxyphenol, hydroquinone, 2,6-di-t-butyl-4 is used as a polymerization inhibitor. A method of reacting at a reaction temperature of 40 to 120 ° C., particularly 60 to 90 ° C., using methylphenol or the like and using dibutyltin dilaurate, dibutyltin diacetate, tin octylate, zinc octylate or the like as a urethanization reaction catalyst Is preferred. When the functional group (c) is an epoxy group and the functional group (d) is a carboxyl group, or the functional group (c) is a carboxyl group, and the functional group (d) is When it is an epoxy group, p-methoxyphenol, hydroquinone, 2,6-di-t-butyl-4-methylphenol or the like is used as a polymerization inhibitor, and tertiary amines such as triethylamine are used as an esterification reaction catalyst. , Quaternary ammoniums such as tetramethylammonium chloride, tertiary phosphines such as triphenylphosphine, quaternary phosphoniums such as tetrabutylphosphonium chloride, etc., and a reaction temperature of 80 to 130 ° C., particularly 100 to The reaction is preferably carried out at 120 ° C.

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

  Since the fluorine-containing polymerizable resin of the present invention obtained as described above can prevent gelation during production and has excellent antifouling properties, its number average molecular weight (Mn) is 1,000 to 10,000. The range is preferable, and the range of 1,500 to 8,000 is more preferable. The weight average molecular weight (Mw) is preferably in the range of 1,500 to 100,000, more preferably in the range of 2,000 to 50,000, and in the range of 2,500 to 20,000. More preferably it is.

  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 Oltech Japan Co., Ltd.)
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

  Furthermore, the polymerizable unsaturated group equivalent in the fluorine-containing polymerizable resin of the present invention is such that the polymerizable unsaturated group equivalent is 200 to 1,500 g / eq. The ratio is preferably from the viewpoint of excellent antifouling properties of the cured coating film, particularly 300 to 700 g / eq. More preferably, it is the range.

  Although the fluorine-containing polymerizable resin of the present invention can be used as a main component of the active energy ray-curable composition itself, it has an extremely excellent surface modification performance. Therefore, the active energy ray-curable composition is used. By adding it as a surface modifier, it is possible to impart excellent scratch resistance to the cured coating film.

  The active energy ray-curable composition of the present invention is a blend of the fluorine-containing polymerizable resin of the present invention, and the main component thereof is an active energy ray-curable resin (E) or active energy ray-curable property. Contains monomer (F). In the active energy ray-curable composition of the present invention, the active energy ray-curable resin (E) and the active energy ray-curable monomer (F) 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 surface modifier in the active energy ray-curable composition.

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

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

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

  Examples of the active energy ray-curable monomer (F) 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 (F) 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 surface modifier, the amount used thereof is the active energy ray-curable resin (E) and the active energy ray-curable resin. It is preferable that it is the range of 0.01-10 mass parts with respect to a total of 100 mass parts of an active monomer (F), and it is more preferable that it is the range of 0.1-5 mass%. 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.

  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. In the case of irradiating ultraviolet rays as active energy rays to form a cured coating film, the photopolymerization initiator (G) is added to the fluorinated 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. It is not necessary to add G) or a photosensitizer.

  Examples of the photopolymerization initiator (G) 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 (G), the compatibility with the active energy ray curable resin (E) and the active energy ray curable monomer (F) 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 (G) 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 per 100 parts by weight of the non-volatile 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 start 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 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, 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, the amount of the organic solvent used varies depending on the intended use and the intended film thickness and viscosity, but is preferably in the range of 0.5 to 50 times the mass of the total mass of the curing component.

  As described above, the active energy ray for curing the active energy ray-curable composition of the present invention is an ionizing radiation such as an ultraviolet ray, an electron beam, an α ray, a β ray, and a γ ray. 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.

  Since the cured coating film of the fluorine-containing polymerizable resin of the present invention has scratch resistance and the like, it can impart scratch resistance to the surface of the article by coating and curing on the surface of the article. In addition, since the fluorine-containing polymerizable resin of the present invention can add leveling properties to the coating material by adding it to the coating material, the active energy ray curing agent composition of the present invention has high leveling properties. Have.

  As an article that can prevent scratches by imparting scratch resistance to the surface using the fluorine-containing polymerizable resin or active energy ray-curable composition of the present invention, polarization of a liquid crystal display (LCD) such as a TAC film can be used. Film for plate; Prism sheet or diffusion sheet as backlight member of LCD; Various display screens (hard coat layer, antireflection layer) such as plasma display (PDP), organic EL display; Touch panel; Electronic terminal such as mobile phone Case or screen; Transparent protective film for color filter for liquid crystal display (hereinafter referred to as “CF”); Organic insulating film for liquid crystal TFT array; Ink-jet ink for forming electronic circuit; Optical recording medium such as CD, DVD, Blu-ray disc ; Transfer film for insert mold (IMD, IMF); Copy machine, pudding Rubber rollers for OA equipment such as-Glass surfaces of reading parts of OA equipment such as copiers and scanners; Optical lenses such as cameras, video cameras and glasses; Windshields and glass surfaces of watches such as watches; Automobiles, railway vehicles, etc. Windows for various vehicles; cover glass or film for solar cells; various building materials such as decorative panels; window glass for houses; woodwork materials for furniture, artificial and synthetic leather, various plastic molded products such as housings for home appliances, FRP bathtubs Etc. 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, the surface of the article is scratch resistant. Can be granted. In addition, it is possible to impart scratch resistance to the surface of an article by adding the fluorine-containing polymerizable resin of the present invention to various paints suitable for each article, and applying and drying.

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: “JNM-ECA500” 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 Oltech Japan Co., Ltd.)
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, by distilling off the solvent under reduced pressure, a compound having a poly (perfluoroalkylene ether) chain represented by the following formula (A-2-1) (hereinafter referred to as “compound (A-2-1)”) Is abbreviated as).

（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 96.7 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, 74 parts by mass of the compound (A-2-1) obtained in Synthesis Example 1 and a polymerizable unsaturated monomer having a silicone group represented by the following formula (B1-1) (hereinafter referred to as “single amount”) (Abbreviated as “body (B1-1)”) 37 parts by mass and 2-hydroxyethyl methacrylate (hereinafter abbreviated as “HEMA”) 45.4 parts by mass in 126 parts by mass of methyl isobutyl ketone, , 3 types of dropping liquids each having 23.5 parts by mass of t-butylperoxy-2-ethylhexanoate as a radical polymerization initiator dissolved in 67.8 parts by mass of methyl isobutyl ketone were separately dropped. It set to the apparatus and it was dripped over 2 hours simultaneously, keeping the inside of a flask at 105 degreeC. After completion of dropping, the mixture was stirred at 105 ° C. for 10 hours to obtain a polymer (P1) solution.

（式中、ｎは平均６５である。）

(Where n is an average of 65)

  A solution of the above polymer (P1) was charged with 0.2 parts by mass of p-methoxyphenol as a polymerization inhibitor and 0.06 parts by mass of tin octylate as a urethanization catalyst, and stirring was started under an air stream. While maintaining the temperature, 49.1 parts by mass of 2-acryloyloxyethyl isocyanate (hereinafter abbreviated as “AOI”) was added dropwise over 1 hour. After completion of the dropwise addition, the mixture was stirred at 60 ° C. for 1 hour, then heated to 80 ° C. and stirred for 10 hours, whereby disappearance of the isocyanate group was confirmed by IR spectrum measurement. Subsequently, methyl isobutyl ketone was added to obtain a methyl isobutyl ketone solution containing 40% by mass of the fluorine-containing polymerizable resin (1). As a result of measuring the molecular weight of the obtained fluorine-containing polymerizable resin (1) by GPC (polystyrene equivalent molecular weight), the number average molecular weight was 2,700, the weight average molecular weight was 8,000, and the polymerizable unsaturated group equivalent was 588 g / eq. Met.

(Example 2)
A glass flask equipped with a stirrer, a thermometer, a condenser, and a dropping device was charged with 84.9 parts by mass of methyl isobutyl ketone as a solvent and heated to 105 ° C. while stirring under a nitrogen stream. Next, 37 parts by mass of the compound (A-2-1) obtained in Synthesis Example 1, 37 parts by mass of the monomer (B1-1) and 63.1 parts by mass of HEMA are dissolved in 132.8 parts by mass of methyl isobutyl ketone. The three types of dripping liquids, the monomer solution and the polymerization initiator solution prepared by dissolving 20.6 parts by mass of t-butylperoxy-2-ethylhexanoate as a radical polymerization initiator in 37 parts by mass of methyl isobutyl ketone, were separately prepared. Were added dropwise over 2 hours while keeping the inside of the flask at 105 ° C. After completion of dropping, the mixture was stirred at 105 ° C. for 10 hours to obtain a polymer (P2) solution.

A solution of the above polymer (P2) was charged with 0.2 parts by mass of p-methoxyphenol as a polymerization inhibitor and 0.06 parts by mass of tin octylate as a urethanization catalyst, and stirring was started under an air stream. While maintaining the temperature, 67.8 parts by mass of AOI was added dropwise over 1 hour. After completion of the dropwise addition, the mixture was stirred at 60 ° C. for 1 hour, then heated to 80 ° C. and stirred for 10 hours, whereby disappearance of the isocyanate group was confirmed by IR spectrum measurement. Subsequently, methyl isobutyl ketone was added to obtain a methyl isobutyl ketone solution containing 40% by mass of the fluorine-containing polymerizable resin (2). As a result of measuring the molecular weight of the obtained fluorine-containing polymerizable resin (2) by GPC (polystyrene equivalent molecular weight), it was found that the number average molecular weight was 2,800, the weight average molecular weight was 7,300, and the polymerizable unsaturated group equivalent was 427 g / eq. Met. In addition, the chart figure of IR spectrum of fluorine-containing polymerizable resin (2) 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 3)
A glass flask equipped with a stirrer, a thermometer, a condenser, and a dropping device was charged with 126.6 parts by mass of methyl isobutyl ketone as a solvent and heated to 105 ° C. while stirring under a nitrogen stream. Next, 17.5 parts by mass of the compound (A-2-1) obtained in Synthesis Example 1, 35 parts by mass of the monomer (B1-1), and 68.1 parts by mass of HEMA were added to 307.4 parts by mass of methyl isobutyl ketone. Of the monomer solution dissolved in 1 and the polymerization initiator solution in which 18.1 parts by mass of t-butylperoxy-2-ethylhexanoate as a radical polymerization initiator was dissolved in 48.2 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 dropping, the mixture was stirred at 105 ° C. for 10 hours to obtain a polymer (P3) solution.

  A solution of the above polymer (P3) was charged with 0.2 parts by mass of p-methoxyphenol as a polymerization inhibitor and 0.06 parts by mass of tin octylate as a urethanization catalyst, and stirring was started under an air stream. While maintaining the temperature, 72.6 parts by mass of AOI was added dropwise over 1 hour. After completion of the dropwise addition, the mixture was stirred at 60 ° C. for 1 hour, then heated to 80 ° C. and stirred for 10 hours, whereby disappearance of the isocyanate group was confirmed by IR spectrum measurement. Subsequently, methyl isobutyl ketone was added to obtain a methyl isobutyl ketone solution containing 40% by mass of the fluorine-containing polymerizable resin (3). As a result of measuring the molecular weight of the obtained fluorine-containing polymerizable resin (3) by GPC (polystyrene equivalent molecular weight), it had a number average molecular weight of 1,500 and a weight average molecular weight of 3,500, and the polymerizable unsaturated group equivalent was 371 g / eq. Met.

Example 4
A glass flask equipped with a stirrer, a thermometer, a condenser, and a dropping device was charged with 133.4 parts by mass of methyl isobutyl ketone as a solvent and heated to 105 ° C. while stirring under a nitrogen stream. Subsequently, 17.8 parts by mass of the compound (A-2-1) obtained in Synthesis Example 1, 53.4 parts by mass of the monomer (B1-1), and 60.8 parts by mass of HEMA were mixed with 334.8 methyl isobutyl ketone. Three types: a monomer solution dissolved in parts by mass and a polymerization initiator solution obtained by dissolving 19.8 parts by mass of t-butylperoxy-2-ethylhexanoate as a radical polymerization initiator in 59.5 parts by mass of methyl isobutyl ketone The dropping liquid was set in separate dropping apparatuses, 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 10 hours to obtain a polymer (P4) solution.

  A solution of the above polymer (P4) was charged with 0.2 parts by mass of p-methoxyphenol as a polymerization inhibitor and 0.06 parts by mass of tin octylate as a urethanization catalyst, and stirring was started under an air stream. While maintaining the temperature, 72.6 parts by mass of AOI was added dropwise over 1 hour. After completion of the dropwise addition, the mixture was stirred at 60 ° C. for 1 hour, then heated to 80 ° C. and stirred for 10 hours, whereby disappearance of the isocyanate group was confirmed by IR spectrum measurement. Subsequently, methyl isobutyl ketone was added to obtain a methyl isobutyl ketone solution containing 40% by mass of the fluorine-containing polymerizable resin (4). As a result of measuring the molecular weight of the obtained fluorine-containing polymerizable resin (4) by GPC (polystyrene equivalent molecular weight), it was found that the number average molecular weight was 1,600, the weight average molecular weight was 4,100, and the polymerizable unsaturated group equivalent was 427 g / eq. Met.

(Example 5)
A glass flask equipped with a stirrer, a thermometer, a condenser, and a dropping device was charged with 158 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, 18 parts by mass of the compound (A-2-1) obtained in Synthesis Example 1, 54 parts by mass of the monomer (B1-1), and 86 parts by mass of glycidyl methacrylate (hereinafter abbreviated as “GMA”). Part of the monomer solution dissolved in 339.3 parts by mass of methyl isobutyl ketone and 23.7 parts by mass of t-butylperoxy-2-ethylhexanoate as a radical polymerization initiator were dissolved in 134.7 parts by mass of methyl isobutyl ketone. Three types of dropping solutions with the polymerization initiator solution were set in separate dropping devices, 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 10 hours to obtain a polymer (P5) solution.

  The solution of the polymer (P5) was heated to 80 ° C. under an air stream, 0.2 parts by mass of p-methoxyphenol was added as a polymerization inhibitor, and 41.4 parts by mass of acrylic acid was added. Further, 1.0 part by mass of triphenylphosphine was added as a catalyst, and the temperature was raised to 120 ° C. and held at 120 ° C. for 9 hours. Subsequently, methyl isobutyl ketone was added to obtain a methyl isobutyl ketone solution containing 10% by mass of the fluorine-containing polymerizable resin (5). 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 1,100, the weight average molecular weight was 4,100, and the polymerizable unsaturated group equivalent was 343 g / eq. Met.

(Comparative Example 1)
A glass flask equipped with a stirrer, thermometer, condenser, and dropping device was charged with 63 parts by mass of methyl isobutyl ketone as a solvent and heated to 105 ° C. while stirring under a nitrogen stream. Next, 21.5 parts by mass of the compound (A-2-1) obtained in Synthesis Example 1, 41.3 parts by mass of HEMA in 334.8 parts by mass of methyl isobutyl ketone, and a radical polymerization initiator Three kinds of dripping liquids with a polymerization initiator solution in which 9.4 parts by mass of t-butylperoxy-2-ethylhexanoate was dissolved in 126 parts by mass of methyl isobutyl ketone were set in separate dripping apparatuses, respectively, While maintaining at 105 ° C., the solution was added dropwise over 2 hours. After completion of dropping, the mixture was stirred at 105 ° C. for 10 hours to obtain a polymer (P6) solution.

  A solution of the above polymer (P6) was charged with 0.1 part by mass of p-methoxyphenol as a polymerization inhibitor and 0.06 part by mass of tin octylate as a urethanization catalyst, and stirring was started under an air stream. While maintaining the temperature, 44.8 parts by mass of AOI was added dropwise over 1 hour. After completion of the dropwise addition, the mixture was stirred at 60 ° C. for 1 hour, then heated to 80 ° C. and stirred for 10 hours, whereby disappearance of the isocyanate group was confirmed by IR spectrum measurement. Subsequently, methyl isobutyl ketone was added to obtain a methyl isobutyl ketone solution containing 40% by mass of the fluorine-containing polymerizable resin (6). As a result of measuring the molecular weight of the obtained fluorine-containing polymerizable resin (6) by GPC (polystyrene equivalent molecular weight), it had a number average molecular weight of 2,400 and a weight average molecular weight of 7,100, and the polymerizable unsaturated group equivalent was 588 g / eq. Met.

(Comparative Example 2)
A glass flask equipped with a stirrer, a thermometer, a condenser, and a dropping device was charged with 45.5 parts by mass of methyl isobutyl ketone as a solvent, and the temperature was raised to 105 ° C. while stirring in a nitrogen stream. Subsequently, 37.4 parts by mass of the compound (A-2-1) obtained in Synthesis Example 1, 5.4 parts by mass of the monomer (B1-1), and 30.8 parts by mass of HEMA were added to 54.6 methyl isobutyl ketone. Three types of dropwise addition of a monomer solution dissolved in parts by mass and a polymerization initiator solution obtained by dissolving 11 parts by mass of t-butylperoxy-2-ethylhexanoate as a radical polymerization initiator in 36.4 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 dropping, the mixture was stirred at 105 ° C. for 10 hours to obtain a polymer (P7) solution.

  A solution of the above polymer (P7) was charged with 0.1 part by mass of p-methoxyphenol as a polymerization inhibitor and 0.03 part by mass of tin octylate as a urethanization catalyst, and stirring was started under an air stream. While maintaining the temperature, 33.2 parts by mass of AOI was added dropwise over 1 hour. After completion of the dropwise addition, the mixture was stirred at 60 ° C. for 1 hour, then heated to 80 ° C. and stirred for 10 hours, whereby disappearance of the isocyanate group was confirmed by IR spectrum measurement. Subsequently, methyl isobutyl ketone was added to obtain a methyl isobutyl ketone solution containing 40% by mass of the fluorine-containing polymerizable resin (7). As a result of measuring the molecular weight of the obtained fluorine-containing polymerizable resin (7) by GPC (polystyrene equivalent molecular weight), the number average molecular weight was 2,400, the weight average molecular weight was 13,000, and the polymerizable unsaturated group equivalent was 427 g / eq. Met.

  Raw materials (mass ratio of the compound (A) and the monomer (B)) of the fluorine-containing polymerizable resins (1) to (7) produced in Examples 1 to 5 and Comparative Examples 1 and 2, Table 1 shows a summary of the number average molecular weight, the weight average molecular weight, and the polymerizable unsaturated group equivalent.

(Example 6)
[Preparation of base resin composition of active energy ray-curable composition]
50 parts by mass of pentafunctional non-yellowing urethane acrylate, 50 parts by mass of dipentaerythritol hexaacrylate, 25 parts by mass of butyl acetate, 5 parts by mass of a photopolymerization initiator (“Irgacure 184” manufactured by BASF Japan Ltd., 1-hydroxycyclohexyl phenyl ketone) Parts of toluene, 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 to dissolve 268 parts by mass of the base resin composition of the active energy ray-curable composition. 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, 2.5 parts by mass (resin content 1 part by mass) of 40% by mass of the fluorine-containing polymerizable resin (1) obtained in Example 1 was added. It mixed uniformly and the active energy ray curable composition was obtained. This active energy ray-curable composition was applied to bar coater No. 13 was applied to an acrylonitrile-butadiene-styrene (ABS) resin plate having a thickness of 2 mm, and then placed in a dryer at 60 ° C. for 5 minutes to volatilize the solvent. Subsequently, the cured coating film was obtained by irradiating the dried coating film with ultraviolet rays using an ultraviolet curing device (under a nitrogen atmosphere, a high-pressure mercury lamp, an ultraviolet irradiation amount of ² kJ / m ² ).

[Strong alkali treatment of cured coatings]
The cured coating film obtained above is 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 subjected to a strong alkali treatment. It was.

[Abrasion resistance test]
Tribogear HEIDON reciprocating wear tester TYPE: 30S (manufactured by Shinto Kagaku Co., Ltd.), wear tester (500g /) with Bonstar No. 0000 (manufactured by Nippon Steel Wool Co., Ltd.) attached to a circular jig with a diameter of 27mm 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 10.
○: The number of scratches is 10 or more and less than 20.
Δ: The number of scratches is 20 or more and less than 50.
X: The number of scratches is 50 or more.

(Examples 7 to 10)
Instead of the fluorine-containing polymerizable resin (1) used in Example 2, the same operation as in Example 2 was carried out except that 1 part by mass of each of the fluorine-containing polymerizable resins (2) to (5) was used as the resin component. The scratch resistance test was conducted.

(Comparative Examples 3 and 4)
Instead of the fluorine-containing polymerizable resin (1) used in Example 2, the same operation as in Example 2 was carried out except that 1 part by mass of the fluorine-containing polymerizable resin (6) or (7) was used as the resin component. A scratch resistance test was conducted.

(Comparative Example 5)
A scratch resistance test was carried out in the same manner as in Example 2 without adding anything to the base resin composition of the active energy ray-curable composition prepared in Example 2.

  Table 1 shows the evaluation results of the scratch resistance tests of Examples 6 to 10 and Comparative Examples 3 to 5.

  Curing coating of the active energy ray-curable composition of Examples 6 to 10 to which the fluorine-containing polymerizable resins (1) to (5) obtained in Examples 1 to 5 which are fluorine-containing polymerizable resins of the present invention were added. It was found that the film has excellent scratch resistance even when treated with a strong alkali.

  On the other hand, Comparative Example 3 is an example in which a fluorine-containing polymerizable resin (6) produced using a polymerizable unsaturated monomer (B) having a silicone group was added to the figure, but the coating surface was damaged. It was found that the scratch resistance after the strong alkali treatment was insufficient.

  Comparative Example 4 shows the mass of the poly (perfluoroalkylene ether) chain of the present invention, the compound (A) having a polymerizable unsaturated group at both ends thereof, and the polymerizable unsaturated monomer (B) having a silicone group. This is an example in which the fluorine-containing polymerizable resin (7) outside the range of 10/90 to 85/15, which is the range of the ratio [(A) / (B)], is added. It was found that the scratch resistance after the treatment with strong alkali was relatively insufficient.

  Comparative Example 5 is an example in which no additive is added and only the active energy ray-curable composition, but the surface of the coating film is easily scratched and the scratch resistance after the strong alkali treatment is insufficient. I understood.

Claims (4)

A poly (perfluoroalkylene ether) chain, a compound (A) having a polymerizable unsaturated group at both ends thereof, a polymerizable unsaturated monomer (B) having a silicone group, and a reactive functional group (c) A functional group (d) having reactivity with the functional group (c) is obtained by polymerizing the polymerizable unsaturated monomer (C) having an essential monomer component with the polymer (P). ) And a compound (D) having a polymerizable unsaturated group, a fluorine-containing polymerizable resin comprising a polymer obtained by reacting,
The mass ratio [(A) / (B)] of the compound (A) and the monomer (B) is in the range of 10/90 to 85/15,
The reactive functional group (c) is at least one reactive 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;
The functional group (d) is reactive to the functional group (c) and at least 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. A fluorine-containing polymerizable resin, which is one functional group.   An active energy ray-curable composition comprising the fluorine-containing polymerizable resin according to claim 1 and an active energy ray-curable resin (E) or an active energy ray-curable monomer (F).   A cured product obtained by applying the fluorine-containing polymerizable resin according to claim 1 or the active energy ray-curable composition according to claim 2 to a substrate and irradiating the active energy ray to cure.   An article having a cured coating film of the fluorine-containing polymerizable resin according to claim 1 or the active energy ray-curable composition according to claim 2.

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