JP2011089052A - Fluorine-containing curable resin, active energy ray-curable composition for coating, and cured product thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a fluorine-containing curable resin that gives excellent antifouling nature to the surface of a cured coating film and a fluorine-containing curable resin that can be used as a fluorine-based surfactant, and further to provide an active energy ray-curable composition for coating that can prevent the fluorine-based surfactant or a decomposition product thereof from vaporizing or coming off from the surface of the coating film after coating and curing and can improve stability of surface characteristics such as antifouling nature; and to provide a cured product thereof. <P>SOLUTION: The fluorine-containing curable resin includes a chain of poly(perfluoroalkylene ether), a radical-polymerizable unsaturated group and a functional group capable of initiating photopolymerization in the resin structure. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

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

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

  A cured coating obtained by applying and curing an active energy ray-curable coating containing this fluorosurfactant or fluorochemical surface modifier (hereinafter simply referred to as “fluorosurfactant”). While the film exhibits excellent surface properties, a part of the fluorosurfactant is removed from the surface of the cured coating film by heating, humidification, exposure to chemicals such as acids and alkalis, and washing to remove dirt. Desorption or volatilization tends to occur, and as a result, the production line is contaminated, and the antifouling property of the coating film surface is lowered.

  For example, in the field of coating materials for protective films such as triacetyl cellulose (TAC) films in polarizing plates for liquid crystal displays, a fluorosurfactant is added to provide antifouling properties against fingerprints and dirt on the film surface. An ultraviolet curable hard coat material is coated on the surface of the protective film. However, the protective film is subjected to a saponification treatment (strong alkali treatment) for the purpose of improving adhesion on the opposite surface to which the hard coat material is applied. At this time, the saponification liquid is applied to the hard coat surface. There was a problem that contact was inevitable, and the fluorosurfactant present in the surface layer was decomposed by strong alkali, resulting in a decrease in antifouling properties.

  In addition, paints and inks for black matrix used for color filters for liquid crystal displays, black resists, and coloring materials that form color pixels of three colors of red, green, and blue are used for liquid repellency after coating film formation. In order to improve the above, an active energy ray-curable resin composition to which a fluorosurfactant is added is used. However, particularly when forming a black matrix by a resist method, after curing by ultraviolet irradiation, heat setting is performed under a high temperature condition of 230 ° C. × 30 minutes. In addition to the volatilization of the part, the liquid repellency of the surface is reduced, and other parts and production lines are contaminated by the volatiles.

  Therefore, in order to prevent such functional degradation of the paint surface, a monoacrylate having a fluorinated alkyl group is copolymerized with an acrylic monomer having active hydrogen, and then the resulting polymer has an isocyanate group. There has been proposed a polymerizable fluorosurfactant having an unsaturated group obtained by reacting an acrylic monomer having benzene (see, for example, Patent Document 1). In addition, a perfluoropolyether group-containing urethane acrylate obtained by reacting a hydroxyl group-containing perfluoropolyether and a hydroxyl group-containing acrylic monomer with a triisocyanate compound that is a diisocyanate trimer is used as a fluorosurfactant. It has been proposed (see, for example, Patent Document 2).

  However, in the polymerization type fluorosurfactant described in Patent Document 1, since the fluorinated alkyl group is bonded to the polymer chain in a pendant form, it is still easily decomposed and detached by the strong alkali treatment described above, and has antifouling properties. In particular, it was difficult to wipe off the dirt once it had adhered, and it was extremely difficult to remove the dirt. On the other hand, the perfluoropolyether group-containing urethane acrylate described in Patent Document 2 can react a hydroxyl group-containing perfluoropolyether and a hydroxyl group-containing acrylic monomer at an appropriate ratio with respect to the trifunctional isocyanate compound. It is difficult to produce a large amount of a compound having only a perfluoropolyether or a compound having only an acryloyl group, so that it is difficult to produce industrially.

JP 2007-246696 A Japanese Patent No. 3963169

  The problem to be solved by the present invention is to provide a fluorine-containing curable resin capable of imparting excellent antifouling properties to the surface of a cured coating film. Moreover, it is providing the fluorine-containing curable resin which can be used as a fluorine-type surfactant. Furthermore, it is possible to prevent volatilization and detachment of the fluorosurfactant or its decomposition product from the coating surface after being applied and cured, and to improve the stability of surface performance such as antifouling property. An active energy ray-curable coating composition and a cured product thereof are provided.

  As a result of intensive studies to solve the above problems, the present inventors have made radical polymerization having a poly (perfluoroalkylene ether) chain, a radical polymerizable unsaturated group, and a functional group having a photopolymerization initiating ability in the resin structure. Volatile resins or those containing radically polymerizable resins in active energy ray-curable coating compositions as fluorine-based surfactants, volatilization or desorption of fluorine-containing curable resins or their decomposition products from cured coatings It was found that surface performance such as antifouling property can be stably imparted to the coating film surface, and the present invention has been completed.

  That is, the present invention is a radical polymerizable resin (I) having a poly (perfluoroalkylene ether) chain, a radical polymerizable unsaturated group, and a functional group having a photopolymerization initiating ability in the resin structure. A fluorine-containing curable resin is provided.

  Furthermore, the present invention provides a cured product obtained by applying the fluorine-containing curable resin to a substrate and irradiating and curing the active energy ray, and an active energy ray-curable coating composition containing the fluorine-containing curable resin. And a cured product obtained by applying the coating composition to a substrate and irradiating it with an active energy ray to be cured.

  The fluorine-containing curable resin of the present invention imparts surface performance such as antifouling property to the cured coating film of the coating composition by blending it into the active energy ray-curable coating composition as a fluorosurfactant. Can do. In addition, the fluorine-containing curable resin of the present invention can volatilize the fluorine-containing curable resin or its decomposition product from the cured coating film by heating, humidification, exposure to chemicals such as acid and alkali, washing for removing dirt, and the like. In addition, since it is difficult for detachment to occur, very stable surface performance such as antifouling property can be imparted to the coating film surface.

  In particular, since the deterioration of the antifouling property after the strong alkali treatment can be suppressed, it is useful for applications where the strong alkali treatment is performed. Specifically, the triacetyl cellulose (TAC) film used for the protective film for polarizing plates of liquid crystal displays is a saponification treatment (strong alkali treatment) for the purpose of improving the adhesiveness of the opposite surface on which the hard coat material is applied. Therefore, by incorporating the fluorine-containing curable resin of the present invention into the active energy ray-curable coating composition used as the hard coat material as a fluorosurfactant, antifouling properties after saponification treatment are obtained. Can be prevented.

  In addition to the hard coat material used for the TAC film, it is useful for protective films that require antifouling properties, antireflection films that are used in flat panel displays such as liquid crystal displays, plasma displays, and organic EL displays, and antiglare films. It is. Moreover, in the hard coat material of the antiglare film, after the hard coat material is cured, the hard coat material is cured by irradiating with an active energy ray from the opposite side of the mold after contacting the mold with the uneven surface shape. It can also be applied to a hard coat material used in a transfer method for embossing the surface.

  Furthermore, a color resist ink for forming each pixel of RGB used for a color filter of a liquid crystal display and a black resist ink for forming a black matrix; a hard coat material used for a touch panel, a mobile phone casing, a liquid crystal display of a mobile phone, etc .; It can be widely used for optical members such as optical fiber clad materials, optical lenses, and optical waveguides.

  Further, since the fluorine-containing curable resin of the present invention has a functional group having a photopolymerization initiating ability in the structure, it can be cured without using a photopolymerization initiator or by reducing the amount of the photopolymerization initiator. Is possible. Therefore, the low molecular weight decomposition product of the radical polymerization initiator after curing causes contamination and is particularly suitable for applications such as IT-related fields in which various properties are deteriorated and building materials that cause problems of sick house syndrome.

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

  The fluorine-containing curable resin of the present invention is a radically polymerizable resin (I) having a poly (perfluoroalkylene ether) chain, a radically polymerizable unsaturated group, and a functional group having a photopolymerization initiating ability in a resin structure. Examples of the method for producing the radical polymerizable resin (I) include the following two methods.

(Method 1)
A compound (A) having a poly (perfluoroalkylene ether) chain and a structural moiety having a radically polymerizable unsaturated group at both ends thereof, and a radically polymerizable unsaturated monomer having a reactive functional group (b) (B To the polymer (P-1) obtained by copolymerizing as an essential monomer component, the functional group (c) reactive with the functional group (b) and a radically polymerizable unsaturated group. A fluorine-containing curable resin by reacting a compound (C) having a functional group (d) having reactivity with the functional group (b) and a functional group (D) having a photopolymerization initiating ability. (The obtained radical polymerizable resin is referred to as “radical polymerizable resin (I-1)”).

(Method 2)
A compound (A) having a poly (perfluoroalkylene ether) chain and a structural moiety having a radically polymerizable unsaturated group at both ends thereof, and a radically polymerizable unsaturated monomer having a reactive functional group (b) (B And a polymer (P-2) obtained by copolymerizing a radically polymerizable unsaturated monomer (E) having a functional group having photopolymerization initiating ability as an essential monomer component, the functional group (B) A method of obtaining a fluorine-containing curable resin by reacting a reactive functional group (c) with a compound (C) having a radically polymerizable unsaturated group (the resulting radically polymerizable resin is referred to as “radical”). Polymerizable resin (I-2) ”).

  First, in the above (Method 1), a compound (A) having a structural part having a poly (perfluoroalkylene ether) chain as a raw material of the fluorine-containing curable resin of the present invention and a radically polymerizable unsaturated group at both ends thereof. ). 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 fluorinated carbon group having 1 to 3 carbon atoms may be one kind or a mixture of plural kinds, and specifically, those represented by the following structural formula 1 may be mentioned. .

（上記構造式１中、Ｘは下記構造式ａ〜ｄであり、構造式１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以上の数である。）

(In the above structural formula 1, X is the following structural formulas a to d, and all X in the structural formula 1 may have the same structure, or a plurality of structures are randomly or block-shaped. And n is a number of 1 or more representing a repeating unit.

  Among these, the perfluoromethylene structure represented by the structural formula a and the structure b are particularly preferred in that the coating film surface has good wiping off of dirt and excellent antifouling properties. Those having a coexisting perfluoroethylene structure are particularly preferred. Here, the abundance ratio between the perfluoromethylene structure represented by the structural formula a and the perfluoroethylene structure represented by the structure b is such that the molar ratio (structure a / structure b) is 1/4 to 4 /. A ratio of 1 is preferable from the viewpoint of antifouling properties, and the value of n in the structural formula 1 is in the range of 3 to 40, particularly 6 to 30.

  The poly (perfluoroalkylene ether) chain is a poly (perfluoroalkylene ether) chain 1 because it has excellent dirt wiping property and slipperiness and is easy to improve the solubility in a non-fluorinated curable resin composition. The total number of fluorine atoms contained in the book is preferably in the range of 18 to 200, and particularly preferably in the range of 25 to 80.

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

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

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

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

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

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

  Next, the radical polymerizable unsaturated monomer (B) having a reactive functional group (b) as a raw material for the fluorine-containing curable resin of the present invention in the (Method 1) will be described. Examples of the monomer (B) include acrylic monomers, aromatic vinyl monomers, vinyl ester monomers, maleimide monomers, and the like. In the present invention, since it is necessary to introduce a radically polymerizable unsaturated group and a functional group having photopolymerization initiating ability into the side chain of the polymer (P-1) using the compound (A) as a raw material, the polymer (P The thing which has a reactive functional group (b) in part or all of monomer components other than the said compound (A) used as the raw material of P-1) is used. In the present invention, as described later, when the radical polymerizable unsaturated monomer (B) is polymerized, it is copolymerized with the compound (A).

  Here, examples of the reactive functional group (b) possessed by the radical polymerizable unsaturated monomer (B) include a hydroxyl group, an isocyanate group, an epoxy group, and a carboxyl group, and the radical polymerizable unsaturated monomer. Examples of the monomer (B) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 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- Hydroxyl group-containing unsaturated monomers such as droxy-3-phenoxypropyl (meth) acrylate, 2- (meth) acryloyloxyethyl-2-hydroxyethyl phthalate, terminal hydroxyl group-containing lactone-modified (meth) acrylate; 2- (meta ) Isocyanate group-containing unsaturated monomers such as acryloyloxyethyl isocyanate, 2- (2- (meth) acryloyloxyethoxy) ethyl isocyanate, 1,1-bis ((meth) acryloyloxymethyl) ethyl isocyanate; glycidyl methacrylate, Epoxy group-containing unsaturated monomers such as 4-hydroxybutyl acrylate glycidyl ether; (meth) acrylic acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl phthalic acid, maleic acid , Itaconic acid, etc. Carboxyl group-containing unsaturated monomers; maleic acid, acid anhydride having an unsaturated double bond such as itaconic anhydride.

  Other radical polymerizable unsaturated monomers that can be copolymerized with the radical polymerizable unsaturated monomer (B) include methyl (meth) acrylate, ethyl (meth) acrylate, (meth) acrylic acid- n-propyl, (meth) acrylic acid-n-butyl, (meth) acrylic acid isobutyl, (meth) acrylic acid-n-pentyl, (meth) acrylic acid-n-hexyl, (meth) acrylic acid-n-heptyl , (Meth) acrylic acid-n-octyl, (meth) acrylic acid-2-ethylhexyl, (meth) acrylic acid nonyl, (meth) acrylic acid decyl, (meth) acrylic acid dodecyl, (meth) acrylic acid cyclohexyl, ( (Meth) acrylic acid esters such as isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, and dicyclopentenyl (meth) acrylate Aromatic vinyls such as styrene, α-methylstyrene, p-methylstyrene, p-methoxystyrene; maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide And maleimides such as phenylmaleimide and cyclohexylmaleimide. These monomers can be used in the same manner in (Method 2) described later.

  Here, the method for producing the polymer (P-1) includes the compound (A), the radical polymerizable unsaturated monomer (B) having a reactive functional group (b), and other if necessary. And a method of polymerizing the radical polymerizable unsaturated monomer in an organic solvent using a radical polymerization initiator. As the organic solvent used here, ketones, esters, amides, sulfoxides, ethers, hydrocarbons are preferable. Specifically, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, butyl acetate, Examples include propylene glycol monomethyl ether acetate, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, toluene, xylene and the like. These are appropriately selected in consideration of boiling point, compatibility, and polymerizability. Examples of the radical polymerization initiator include peroxides such as benzoyl peroxide and azo compounds such as azobisisobutyronitrile. Furthermore, chain transfer agents such as lauryl mercaptan, 2-mercaptoethanol, thioglycerol, ethylthioglycolic acid, octylthioglycolic acid and the like can be used as necessary.

  The molecular weight of the obtained polymer (P-1) needs to be in a range in which crosslinking insolubilization does not occur during polymerization, and crosslinking insolubilization may occur if the molecular weight is too high. Within that range, the polymer (P-1) has a number average molecular weight (Mn) of 800 to 3 in that the number of polymerizable unsaturated groups in one molecule of the finally obtained radical polymerizable resin increases. Preferably in the range of 1,000 to 2,500, and the weight average molecular weight (Mw) in the range of 1,500 to 40,000, particularly 2,000 to 30,000. preferable.

  In the polymer (P-1) obtained as described above, the compound (C) having a functional group (c) having reactivity with the functional group (b) and a radical polymerizable unsaturated group, and the functional group The target radical polymerizable resin (I-1) is obtained by reacting the functional group (d) having reactivity with the group (b) and the compound (D) having a functional group having photopolymerization initiating ability. It is done.

  As a functional group (c) which the said compound (C) has, a hydroxyl group, an isocyanate group, an epoxy group, a carboxyl group etc. are mentioned, for example. In the case where the functional group (b) is a hydroxyl group, examples of the functional group (c) include an isocyanate group, a carboxyl group, a carboxylic acid halide group, and an epoxy group, and the reactive functional group (b) is an isocyanate group. In the case where the functional group (c) includes a hydroxyl group and the reactive functional group (b) is an epoxy group, the functional group (c) includes a carboxyl group and a hydroxyl group, and the reactive functional group (b). When is a carboxyl group, examples of the functional group (c) include an epoxy group and a hydroxyl group. In particular, the functional group (b) of the monomer (B) is an isocyanate group and the functional group (c) of the compound (C) is a hydroxyl group, or the monomer (B) It is preferable that the functional group (b) possessed by is a hydroxyl group and the functional group (c) possessed by the compound (C) is an isocyanate group since the reaction proceeds smoothly.

  As such a compound (C), specifically, the same compounds as those exemplified as the radical polymerizable unsaturated monomer (B) having the reactive functional group (b) can be used. Other examples include 2-hydroxy-3-acryloyloxypropyl methacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate and the like.

  Of these, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, 4-hydroxybutyl acrylate, 1,4- Cyclohexanedimethanol monoacrylate, N- (2-hydroxyethyl) acrylamide, 2-acryloyloxyethyl isocyanate, 4-hydroxybutyl acrylate glycidyl ether, and acrylic acid are preferred.

  The functional group (d) possessed by the compound (D) is selected according to the type of the reactive functional group (b), similarly to the functional group (c) possessed by the compound (C). In particular, the functional group (b) of the monomer (B) is an isocyanate group and the functional group (d) of the compound (D) is a hydroxyl group, or the monomer (B) It is preferable that the functional group (b) possessed by is a hydroxyl group and the functional group (d) possessed by the compound (D) is an isocyanate group since the reaction proceeds smoothly.

  In addition, the functional group having the photopolymerization initiating ability of the compound (D) can be used without particular limitation as long as it is a functional group having a photopolymerization initiating ability. Even things can be used. Among these, the intramolecular cleavage type is more preferable.

  Examples of functional groups having an intramolecular cleavage type photopolymerization initiating ability include those having a benzophenone skeleton, those having a thioxanthone skeleton, those having a benzoin skeleton, those having a benzyldimethyl ketal skeleton, and an α-hydroxyalkylphenone skeleton , Those having an α-aminoalkylphenone skeleton, those having an acylphosphine oxide skeleton, those having an alclephenylglyoxylate skeleton, those having a diethoxyacetophenone skeleton, and the like.

  When the said compound (D) is illustrated with structural formula, what has the following structural formula will be mentioned.

（式中、Ｒはアルキル基又はフェニル基を有するアルキル基を表し、Ｌは２価の有機基を表し、（ｄ）は前記単量体（Ｂ）が有する反応性官能基（ｂ）と反応性を有する官能基（ｄ）を表す。なお、式中の芳香環は置換基を有していてもよく、また、−Ｌ−（ｄ）は上記の構造式で示した芳香環以外の芳香環に結合していてもよい。）

(In the formula, R represents an alkyl group or an alkyl group having a phenyl group, L represents a divalent organic group, and (d) reacted with the reactive functional group (b) of the monomer (B)). The aromatic ring in the formula may have a substituent, and -L- (d) is an aromatic other than the aromatic ring shown in the above structural formula. (It may be bonded to the ring.)

  Specific examples of the compound (D) include 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one.

  The method of reacting the compound (C) and the compound (D) with the polymer (P-1) is performed under the condition that the radically polymerizable unsaturated group in the compound (C) and the compound (D) is not polymerized. For example, the reaction is preferably performed by adjusting the temperature condition to a range of 30 to 120 ° C. This reaction is preferably carried out in the presence of a catalyst or a polymerization inhibitor, and if necessary in the presence of an organic solvent.

  For example, when the functional group (b) is a hydroxyl group and the functional group (c) is an isocyanate group, or the functional group (b) is an isocyanate group and the functional group (c) is a hydroxyl group. In this case, p-methoxyphenol, hydroquinone, 2,6-di-t-butyl-4-methylphenol or the like is used as a polymerization inhibitor, and dibutyltin dilaurate, dibutyltin diacetate, tin octylate, A method in which zinc octylate or the like is used and the reaction is performed at a reaction temperature of 40 to 120 ° C., particularly 60 to 90 ° C. is preferable. When the functional group (b) is an epoxy group and the functional group (c) is a carboxyl group, or the functional group (b) is a carboxyl group and the functional group (c) is an epoxy group. In this case, 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. Using a quaternary ammonium such as tetramethylammonium, a tertiary phosphine such as triphenylphosphine, a quaternary phosphonium such as tetrabutylphosphonium chloride, etc., and a reaction temperature of 80 to 130 ° C., particularly 100 to 120 ° C. It is preferable to make it react with.

  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.

  Next, (Method 2) for obtaining the radical polymerizable resin (I-2) will be described. The compound (A) having a poly (perfluoroalkylene ether) chain used in (Method 2) and a structural moiety having a radical polymerizable unsaturated group at both ends thereof is the same as the compound (A) used in (Method 1) Similar ones can be used. Further, the same monomer (B) and compound (C) as those used in (Method 1) can be used.

  In (Method 2), the radical polymerizable unsaturated monomer (E) having a functional group having photopolymerization initiating ability used as a raw material will be described. Examples of the monomer (E) include acrylic monomers, aromatic vinyl monomers, vinyl ester monomers, maleimide monomers, and the like. Moreover, the functional group which has the photoinitiating ability which this monomer (E) has can use the same thing as the functional group which has the photoinitiating ability which the said compound (D) has. When the said monomer (E) is illustrated with structural formula, what has the following structural formula will be mentioned.

（式中、Ｒはアルキル基又はフェニル基を有するアルキル基を表し、Ｌは２価の有機基を表し、Ｕはラジカル重合性不飽和基を表す。なお、式中の芳香環は置換基を有していてもよく、また、−Ｌ−Ｕは上記の構造式で示した芳香環以外の芳香環に結合していてもよい。）

(In the formula, R represents an alkyl group or an alkyl group having a phenyl group, L represents a divalent organic group, U represents a radically polymerizable unsaturated group, and the aromatic ring in the formula represents a substituent. And -L-U may be bonded to an aromatic ring other than the aromatic ring shown in the above structural formula.)

  The radically polymerizable unsaturated group (“U” in the above formula) possessed by the monomer (E) is preferably a (meth) acryloyl group. Moreover, the following monomers (E-1)-(E-6) are mentioned as a more specific example of the said monomer (E).

  In addition to the monomer (E), 4- (13-acryloyl-1,4,7,10,13-pentaoxatridecyl) -benzophenone, 4- (13-methacryloyl-1,4,7, And 10,13-pentaoxatridecyl) -benzophenone.

  In (Method 2), the method for producing the polymer (P-2) includes the compound (A), a radical polymerizable unsaturated monomer (B) having a reactive functional group (b), and , The above-mentioned polymer (P-1) using a radically polymerizable unsaturated monomer (E) having a functional group having photopolymerization initiating ability and further using another radically polymerizable unsaturated monomer if necessary. The same method as the manufacturing method of is mentioned.

  The molecular weight of the obtained polymer (P-2) needs to be in a range where crosslinking insolubilization does not occur during polymerization, and crosslinking insolubilization may occur if the molecular weight is too high. Within that range, the polymer (P-2) has a number average molecular weight (Mn) of 800 to 3 in that the number of polymerizable unsaturated groups in one molecule of the finally obtained radical polymerizable resin increases. Preferably in the range of 1,000 to 2,500, and the weight average molecular weight (Mw) in the range of 1,500 to 40,000, particularly 2,000 to 30,000. preferable.

  Moreover, the target radically polymerizable resin (I-2) can be obtained by performing reaction with the said compound (C) when manufactured similarly to (Method 1). At this time, as in (Method 1), in particular, the functional group (b) of the monomer (B) (the reactive functional group (b) of the polymer (P-2)) is an isocyanate group. And the functional group (c) of the compound (C) is a hydroxyl group, or the functional group (b) of the monomer (B) (reactive functional group of the polymer (P-2)). It is preferable that (b)) is a hydroxyl group and the functional group (c) of the compound (C) is an isocyanate group because the reaction proceeds smoothly.

  The number average molecular weight (Mn) of the radical polymerizable resin (I) obtained as the radical polymerizable resin (I-1) or (I-2) by the above (Method 1) or (Method 2) is 1,000 to It is preferably in the range of 5,000, more preferably in the range of 1,500 to 4,000. Further, the weight average molecular weight (Mw) is preferably in the range of 3,000 to 50,000, and more preferably in the range of 4,000 to 40,000. By setting Mn and Mw of the radical polymerizable resin (I) within these ranges, gelation during the production of the radical polymerizable resin (I) can be prevented, and the coating performance with excellent cross-linking and excellent antifouling properties. Can be expressed.

  Here, the number average molecular weight (Mn) and the weight average molecular weight (Mw) are values converted to polystyrene based on gel permeation chromatography (GPC) measurement. The measurement conditions for GPC are described in the examples.

  The radical polymerizable resin (I) preferably has a fluorine content, which is a content ratio of fluorine atoms contained in the resin, in the range of 2 to 35% by mass from the viewpoint of antifouling property of the cured coating film.

  The fluorine-containing curable resin of the present invention, which is the radical polymerizable resin (I), can be used as a main component of the active energy ray-curable coating composition, but has extremely excellent surface modification performance. Therefore, the antifouling property which was excellent in the cured coating film can be provided by using as a fluorine-type surfactant added to an active energy ray hardening-type coating composition.

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

  Examples of the active energy ray-curable resin (II) include urethane (meth) acrylate resins, unsaturated polyester resins, epoxy (meth) acrylate resins, polyester (meth) acrylate resins, and acrylic (meth) acrylate resins. In the present invention, a urethane (meth) acrylate resin is particularly preferable from the viewpoints of transparency and low shrinkage.

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

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

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

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

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

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

  Next, as an epoxy vinyl ester resin, (meth) acrylic acid is reacted with an epoxy group of an epoxy resin such as a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a phenol novolac type epoxy resin, or a cresol novolak type epoxy resin. What is obtained is mentioned. These active energy ray-curable resins (II) can be used alone or in combination of two or more.

  Examples of the active energy ray-curable monomer (III) 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-hexanedio Rudi (meth) acrylate, hydroxypivalate ester neopentyl glycol di (meth) acrylate, bisphenol A di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythr Tall 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 ( ) Acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, aliphatic alkyl (meth) acrylate such as 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- (Dimethylamino) ethyl (meth) acrylate, γ- (meth) acryloxypropyltrimethoxysilane, 2-methoxyethyl (meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxy Dipropylene glycol (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, nonylphenoxypolypropylene glycol (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydipropylene glycol (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, di Cyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate Rate, isobornyl (meth) acrylate, methoxylated tricyclodecanyloxy triene (meth) acrylate, phenyl (meth) acrylate.

  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 (III) can be used alone or in combination of two or more.

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

  The fluorine-containing curable resin or active energy ray-curable coating composition of the present invention can be formed into a cured coating film by irradiating active energy rays after being applied to a substrate. The active energy rays refer to ionizing radiation such as ultraviolet rays, electron beams, α rays, β rays, and γ rays. When ultraviolet rays are used as the active energy ray, the fluorine-containing curable resin of the present invention has a functional group having a photopolymerization initiating ability in the resin structure, so that it can be cured without adding a photopolymerization initiator. Although it is possible, it is preferable to add a photoinitiator (IV) in a fluorine-containing curable resin or an active energy ray hardening-type composition as needed, and to improve sclerosis | hardenability further. Further, if necessary, a photosensitizer can be added to improve curability.

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

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

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

  Furthermore, the fluorine-containing curable resin or active energy ray-curable coating composition of the present invention can be used for adjusting the viscosity or refractive index or coating the coating composition within a range that does not impair the effects of the present invention, depending on the purpose of use, characteristics, etc. Various compounding materials for the purpose of adjusting film color tone and other paint properties and coating film properties, such as various organic solvents, acrylic resins, phenol resins, polyester resins, polystyrene resins, urethane resins, urea resins, melamine resins , Various resins such as alkyd resin, epoxy resin, polyamide resin, polycarbonate resin, petroleum resin, fluorine resin, PTFE (polytetrafluoroethylene), polyethylene, polypropylene, carbon, titanium oxide, alumina, copper, silica fine particles Organic or inorganic particles, polymerization initiators, polymerization inhibitors, antistatic agents, antifoaming agents, viscosity modifiers, Stabilizer, weather stabilizer, heat stabilizer, antioxidant, rust inhibitor, slip agent, wax, gloss adjuster, mold release agent, compatibilizer, conductivity modifier, pigment, dye, dispersant, dispersion stabilizer , Silicone-based and hydrocarbon-based surfactants can be used in combination.

  In each of the above ingredients, the organic solvent is useful in appropriately adjusting the solution viscosity of the fluorine-containing curable resin or active energy ray-curable coating composition of the present invention, and particularly for performing thin film coating. It becomes easy to adjust the film thickness. 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 application and the target film thickness and viscosity, but is preferably in the range of 0.5 to 2 times the mass of the total mass of the curing component.

  As described above, the active energy ray for curing the fluorine-containing curable resin or the active energy ray-curable coating composition of the present invention is ionizing radiation such as ultraviolet rays, electron beams, α rays, β rays, and γ rays. However, as specific energy sources or curing devices, for example, germicidal lamps, fluorescent lamps for ultraviolet rays, carbon arc, xenon lamps, high pressure mercury lamps for copying, medium or high pressure mercury lamps, ultrahigh pressure mercury lamps, electrodeless lamps, metal halide lamps UV light using natural light as a light source, or an electron beam using a scanning type or curtain type electron beam accelerator.

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

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

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

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

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

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

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

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

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

  Hereinafter, the present invention will be described in more detail with reference to specific examples.

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

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

[GPC measurement conditions]
Measuring device: “HLC-8220 GPC” manufactured by Tosoh Corporation
Column: Guard column “HHR-H” manufactured by Tosoh Corporation (6.0 mm ID × 4 cm)
+ "TSK-GEL GMHHR" (7.8 mm ID x 30 cm) manufactured by Tosoh Corporation
+ "TSK-GEL GMHHR" (7.8 mm ID x 30 cm) manufactured by Tosoh Corporation
+ "TSK-GEL GMHHR" (7.8 mm ID x 30 cm) manufactured by Tosoh Corporation
+ "TSK-GEL GMHHR" (7.8 mm ID x 30 cm) manufactured by Tosoh Corporation
Detector: ELSD ("ELSD2000" manufactured by Oltec)
Data processing: “GPC-8020 Model II version 4.10” manufactured by Tosoh Corporation
Measurement conditions: Column temperature 40 ° C
Developing solvent Tetrahydrofuran
Flow rate 1.0 ml / min Standard sample: The following monodisperse polystyrene having a known molecular weight was used in accordance with the measurement manual of “GPC-8020 model II version 4.10”.

(Polystyrene used)
“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
Sample: A 1.0 mass% tetrahydrofuran solution in terms of resin solid content filtered through a microfilter (100 μl).

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

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

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

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

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

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

Example 1
A glass flask equipped with a stirrer, a thermometer, a condenser, and a dropping device was charged with 110.7 parts by mass of methyl isobutyl ketone as a solvent, and the temperature was raised to 95 ° C. while stirring in a nitrogen stream. Next, 37.9 parts by mass (Liquid 1) of the monomer (A-1-1) obtained in Synthesis Example 1 above and 72.3 parts by mass of 2-methacryloyloxyethyl isocyanate were converted to 54.0 parts by mass of methyl isobutyl ketone. 126.3 parts by mass (solution 2) dissolved in 1 part and 16.7 parts by mass of 2,2′-azobis (2-methylbutyronitrile) as a radical polymerization initiator were added to 40.4 parts by mass of methyl isobutyl ketone. 3 drops of the solution dissolved in 57.1 parts by mass (Liquid 3) were set in separate dropping devices, and the dropping was started at the same time while maintaining the inside of the flask at 95 ° C. The liquid 3 was dripped over 2 hours and 20 minutes for 2 hours. After completion of dropping, the mixture was stirred at 95 ° C. for 10 hours, and then the solvent was distilled off to obtain a polymer (P-1-1).

  Next, 151.2 parts by mass of methyl ethyl ketone as a solvent, 0.067 parts by mass of p-methoxyphenol as a polymerization inhibitor, 2,6-di-t-butyl- were added to the polymer (P-1-1) obtained above. 4-Methylphenol 0.5 part by mass, 0.05 part by mass of tin octylate as a urethanization catalyst was charged, stirring was started under an air stream, and 46.8 parts by mass of 2-hydroxyethyl acrylate was maintained at 60 ° C. 10. 50.8 parts by mass of solution (Liquid 4) dissolved in 4 parts by mass of MEK and 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one Two types of dripping liquids, 210.3 parts by mass (Liquid 5), in which 1 part by mass was dissolved in 200.2 parts by mass of methyl ethyl ketone, were set in separate dripping devices, both taking 1 hour. The dropped. After completion of the dropwise addition, the mixture was stirred at 60 ° C. for 2 hours, heated to 80 ° C. and stirred for 4 hours, and the disappearance of the absorption peak of the isocyanate group was confirmed by IR spectrum measurement of the reaction solution.

After cooling said reaction liquid to room temperature, the thing insoluble in a solution was separated by filtration, and the methyl ethyl ketone solution containing 39.7 mass% of radical polymerizable resin (I-1-1) was obtained. As a result of measuring the molecular weight of this radical polymerizable resin (I-1-1) by GPC (polystyrene conversion molecular weight), the number average molecular weight was 2,600, the weight average molecular weight was 28,000, and the maximum molecular weight was 1,000,000. The fluorine content was 12.8% by mass. FIG. 1 shows a chart of the IR spectrum of the obtained radical polymerizable resin (I-1-1), FIG. 2 shows a chart of ¹³ C-NMR, and FIG. 3 shows a chart of GPC.

(Comparative Example 1)
A glass flask equipped with a stirrer, a thermometer, a condenser, and a dropping device was charged with 69 parts by mass of methyl isobutyl ketone as a solvent and heated to 105 ° C. while stirring under a nitrogen stream. Subsequently, 40 parts by mass of an acrylate having a fluorinated alkyl group represented by the following formula (Y-1) and 28.8 parts by mass of 2-hydroxyethyl methacrylate, and 69 parts by mass of methyl isobutyl ketone as a solvent 135.8 parts by mass of a body solution, 25.9 parts by mass of an initiator solution in which 3.4 parts by mass of t-butylperoxy-2-ethylhexanoate as a radical polymerization initiator and 22.5 parts by mass of methyl isobutyl ketone as a solvent were mixed. The two types of dripping liquids were set in separate dripping devices, and dripped simultaneously over 3 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 232.7 parts by mass of a polymer solution.

  Next, 0.1 parts by mass of p-methoxyphenol as a polymerization inhibitor and 0.05 parts by mass of tin octylate as a urethanization catalyst were charged into the polymer solution obtained above, while maintaining 60 ° C. in an air stream. 31.2 parts by mass of 2-acryloyloxyethyl isocyanate was added dropwise over 1 hour. After completion of the dropwise addition, the mixture was stirred at 60 ° C. for 1 hour, then heated to 80 ° C. and stirred for 10 hours. As a result, the disappearance of the isocyanate group was confirmed by IR spectrum measurement. Subsequently, a part of the solvent was distilled off under reduced pressure to obtain 203.4 parts by mass of a methyl isobutyl ketone solution containing 50% by mass of the radical polymerizable resin (Z-1). The molecular weight of the radical polymerizable resin (Z-1) was measured by GPC (polystyrene equivalent molecular weight). As a result, the number average molecular weight was 3,000, the weight average molecular weight was 7,000, and the maximum molecular weight was 40,000.

(Preparation of base resin composition of active energy ray-curable coating 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, 1-hydroxycyclohexyl phenyl ketone (“Irgacure 184” manufactured by Ciba Specialty Chemicals) as a photopolymerization initiator 5 The base resin composition of the active energy ray-curable coating composition is prepared by mixing and dissolving 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 as a solvent. Got.

(Example 2, Comparative Examples 2-3)
To the 268 parts by mass of the base resin composition obtained above, the radically polymerizable resin solution obtained in Example 1 and Comparative Example 1 was added in an amount of 1 part by mass as a resin component, and the mixture was uniformly mixed. An energy ray curable coating composition was obtained. Next, this active energy ray-curable coating composition was applied to a bar coater No. 13 using, after application to TAC film having a thickness of 80 [mu] m, placed in a 60 ° C. oven for 5 minutes to evaporate the solvent, ultraviolet curing device (in a nitrogen atmosphere, a high-pressure mercury lamp used, the amount of ultraviolet irradiation 2 kJ / m ² ) To produce a coated film as Example 2 and Comparative Example 2. Moreover, the coating film was similarly produced about the active energy ray hardening-type coating composition which has not added fluorine-containing curable resin, and it was set as the comparative example 3.

  On the coated surface of the resulting coated film, draw a line with a felt-tip pen (Magic Ink Large Blue manufactured by Teranishi Chemical Industry Co., Ltd.) and visually observe the blue ink adhering state (antifouling) Evaluation of prevention property and dirt wiping property was performed. The evaluation criteria are as follows.

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

[Evaluation criteria for wiping off dirt]
After the “stain adhesion prevention” test, the appearance when wiped off with a load of 1 kg was evaluated according to the following criteria.
○: The ink can be completely removed by wiping once.
Δ: The ink was completely removed by wiping 2 to 10 times.
X: The ink could not be completely removed by 10 wiping operations.

  In addition, after UV curing, the film was immersed in a strong alkaline aqueous solution (2 mol / l KOH aqueous solution) at 70 ° C. for 1 minute, washed with pure water, dried at 100 ° C. × 3 minutes, and then allowed to cool at room temperature. The coated film was also evaluated for antifouling properties (stain adhesion prevention, dirt wiping properties) using a felt pen in the same manner as described above.

  The evaluation results are shown in Table 1.

  The cured coating film of the active energy ray-curable coating composition of Example 2 to which the radical polymerizable resin obtained in Example 1 which is a fluorine-containing curable resin of the present invention is added may be treated with strong alkaline water. The soil adhesion prevention property and the soil wiping property did not deteriorate. On the other hand, in Comparative Example 2 using the radical polymerizable resin (Z-1), a decrease was observed in the soil adhesion preventing property and soil wiping property after treatment with strong alkaline water. In Comparative Example 3 in which nothing was added, the stain adhesion preventing property and the stain wiping property were poor both before and after the treatment with strong alkaline water.

Claims (12)

  A fluorine-containing curable resin comprising a radically polymerizable resin (I) having a poly (perfluoroalkylene ether) chain, a radically polymerizable unsaturated group, and a functional group having a photopolymerization initiating ability in a resin structure.   A compound (A) having a poly (perfluoroalkylene ether) chain and a structural moiety having a radically polymerizable unsaturated group at both ends thereof, and a radically polymerizable unsaturated monomer having a reactive functional group (b) (B To the polymer (P-1) obtained by copolymerizing as an essential monomer component, the functional group (c) having reactivity with the functional group (b) and a radical polymerizable unsaturated group. Radical polymerizable resin obtained by reacting compound (C) having a functional group (d) having reactivity with the functional group (b) and a compound (D) having a photopolymerization initiating ability The fluorine-containing curable resin according to claim 1, which is (I-1).   The reactive functional group (b) of the radical polymerizable unsaturated monomer (B) is an isocyanate group, and the functional group (c) of the compound (C) and the functional group of the compound (D). (D) is a hydroxyl group, or the reactive functional group (b) of the radical polymerizable unsaturated monomer (B) is a hydroxyl group and the functional group (c) of the compound (C) And the functional group (d) of the compound (D) is an isocyanate group.   The fluorine-containing curable resin according to claim 2 or 3, wherein the functional group having the photopolymerization initiating ability of the compound (D) is a functional group having an α-hydroxyalkylphenone skeleton.   A compound (A) having a poly (perfluoroalkylene ether) chain and a structural moiety having a radically polymerizable unsaturated group at both ends thereof, and a radically polymerizable unsaturated monomer having a reactive functional group (b) (B And a polymer (P-2) obtained by copolymerizing a radically polymerizable unsaturated monomer (E) having a functional group having photopolymerization initiating ability as an essential monomer component, the functional group The radically polymerizable resin (I-2) obtained by reacting the compound (C) having a functional group (c) having reactivity with (b) and a radically polymerizable unsaturated group. Fluorine curable resin.   The reactive functional group (b) of the radical polymerizable unsaturated monomer (B) is an isocyanate group and the functional group (c) of the compound (C) is a hydroxyl group, or the radical The fluorine-containing curing according to claim 5, wherein the reactive functional group (b) of the polymerizable unsaturated monomer (B) is a hydroxyl group, and the functional group (c) of the compound (C) is an isocyanate group. Resin.   The fluorine-containing curable resin according to claim 5 or 6, wherein the functional group having photopolymerization initiating ability of the radical polymerizable unsaturated monomer (E) is a functional group having an α-hydroxyalkylphenone skeleton.   The fluorine-containing curable resin according to any one of claims 1 to 7, wherein the poly (perfluoroalkylene ether) chain contained in the resin structure contains 25 to 80 fluorine atoms per chain.   A cured product obtained by applying the fluorine-containing curable resin according to any one of claims 1 to 8 to a substrate and irradiating the substrate with an active energy ray to be cured.   An activity comprising the fluorine-containing curable resin according to any one of claims 1 to 8, and the active energy ray curable resin (II) or the active energy ray curable monomer (III). Energy ray curable coating composition.   The active energy ray hardening-type coating composition of Claim 10 which uses the fluorine-containing curable resin of any one of Claims 1-8 as a fluorine-type surfactant or a fluorine-type surface modifier.   A cured product obtained by applying the active energy ray-curable coating composition according to claim 10 or 11 to a substrate and irradiating and curing the active energy ray.

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