JP5397686B2 - Fluorine-containing curable resin, active energy ray-curable coating composition and cured product thereof - Google Patents

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, in a normal production line that irradiates ultraviolet rays after coating, there are many cases where ultraviolet rays are irradiated in an air atmosphere, and there is a problem in that polymerization is inhibited by oxygen present in the air and the antifouling property is lowered. .

  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. In addition, when cured by irradiating with ultraviolet rays in an air atmosphere (in the presence of oxygen), there is a problem that sufficient antifouling properties cannot be exhibited.

  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 that it can impart excellent antifouling properties to the surface of the cured coating film, and can exhibit excellent antifouling properties even when cured in an air atmosphere (in the presence of oxygen). It is to provide a fluorine-containing curable resin. 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 desorption 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 capable of exhibiting excellent antifouling properties even when cured in an air atmosphere and a cured product thereof.

  As a result of intensive studies to solve the above problems, the present inventors have obtained a fluorine-containing curable resin having a poly (perfluoroalkylene ether) chain and a maleimide group in the resin structure, or the fluorine-containing curable resin. When blended with an active energy ray-curable coating composition as a fluorosurfactant, the volatilization and detachment of the fluorinated curable resin or its decomposition products from the cured coating can be suppressed, and the coating surface is antifouling. The present inventors have found that the surface performance such as the above can be stably imparted and excellent antifouling properties can be exhibited even when cured in an air atmosphere, and the present invention has been completed.

That is, the present invention is a curable fluorine-containing resin that having a poly (perfluoroalkylene ether) chain and a maleimide group in the resin structure, the fluorine-containing curable resin is poly (perfluoroalkylene ether) chain and its An essential monomer component comprising a compound (A) having a structural moiety having a radically polymerizable unsaturated group at both ends and a radically polymerizable unsaturated monomer (B) having a maleimide group having no radically polymerizable property The present invention provides a fluorine-containing curable resin characterized in that it is a radically polymerizable resin obtained by copolymerization.
The present invention is also a fluorine-containing curable resin having a poly (perfluoroalkylene ether) chain and a maleimide group in the resin structure, and the fluorine-curable resin is attached to the poly (perfluoroalkylene ether) chain and both ends thereof. A compound (A) having a structural site having a radically polymerizable unsaturated group and a radically polymerizable unsaturated monomer (C) having a reactive functional group (c) are copolymerized as essential monomer components. A fluorine-containing product obtained by reacting the polymer (P2) obtained by reacting a compound (E) having a functional group (e) and a maleimide group having reactivity with the functional group (c). A 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 imparts very stable surface performance such as antifouling property to the coating film surface even when cured by irradiation with ultraviolet rays in an air atmosphere (in the presence of oxygen). Can do.

  Therefore, the fluorine-containing curable resin of the present invention and the active energy ray-curable coating composition containing the same are discharged under a nitrogen purged nitrogen atmosphere in order to discharge air from the inside of the curing device that irradiates active energy rays such as ultraviolet rays. There is an advantage that sufficient performance can be exhibited not only in the case of curing, but also in the case where nitrogen purging is difficult due to manufacturing cost, apparatus restrictions, and the like.

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

  The fluorine-containing curable resin of the present invention has a poly (perfluoroalkylene ether) chain and a maleimide group in the resin structure. As a manufacturing method of this fluorine-containing curable resin, the following method etc. are mentioned, for example.

(Method 1)
First, as (Method 1), a compound (A) having a poly (perfluoroalkylene ether) chain and a structure part having a radically polymerizable unsaturated group at both ends thereof, and a radical having a maleimide group having no radically polymerizable property A method of obtaining a fluorine-containing curable resin by copolymerizing a polymerizable unsaturated monomer (B) as an essential monomer component (the obtained fluorine-containing curable resin is referred to as “fluorine-containing curable resin (V1)”). ").).

(Method 1 ')
Further, as (Method 1 ′), a compound (A) having a structural site having a radically polymerizable unsaturated group at both ends of the poly (perfluoroalkylene ether) chain of the above (Method 1), radical polymerization In the copolymerization with the radically polymerizable unsaturated monomer (B) having a maleimide group not having a radical, the radically polymerizable unsaturated monomer having a reactive functional group (c) in addition to the monomer (B) A functional group (d) having reactivity with the functional group (c) and an active energy ray-curable group are added to the polymer (P1) obtained by copolymerizing the monomer (C) as a monomer component. A method for obtaining a fluorine-containing curable resin by reacting the compound (D) having the compound (D) is referred to as “fluorine-containing curable resin (V1 ′)”. This fluorine-containing curable resin (V1 ′) has a maleimide group and an active energy ray-curable group other than the maleimide group as a curable functional group.

(Method 2)
On the other hand, as (Method 2), a compound (A) having a poly (perfluoroalkylene ether) chain and a structural moiety having a radical polymerizable unsaturated group at both ends thereof, and radical polymerization having a reactive functional group (c) A functional group (e) having a reactivity with the functional group (c) and a maleimide to a polymer (P2) obtained by copolymerizing a polymerizable unsaturated monomer (C) as an essential monomer component And a method of reacting a group-containing compound (E) to obtain a fluorine-containing curable resin (the resulting fluorine-containing curable resin is referred to as “fluorine-containing curable resin (V2)”).

(Method 2 ')
Further, as (Method 2 ′), the compound (P2) obtained by the above (Method 2) is combined with a compound having a functional group (e) having a reactivity with the functional group (c) and a maleimide group ( A method of obtaining a fluorine-containing curable resin by reacting a compound (D) having a functional group (d) having reactivity with the functional group (c) and an active energy ray-curable group in addition to E) (The obtained fluorine-containing curable resin is referred to as “fluorine-containing curable resin (V2 ′)”). This fluorine-containing curable resin (V2 ′) has a maleimide group and an active energy ray-curable group other than the maleimide group as a curable functional group.

  First, the compound (A) having a poly (perfluoroalkylene ether) chain as a raw material of the fluorine-containing curable resin of the present invention and a structural site having a radically polymerizable unsaturated group at both ends thereof will be described. Examples of the poly (perfluoroalkylene ether) chain of the compound (A) include those having a structure in which divalent fluorocarbon groups having 1 to 3 carbon atoms and oxygen atoms are alternately connected. The divalent 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, A-2, A are particularly easy because the industrial production of the compound (A) itself is easy and the polymerization reaction when producing the polymer (P1) is also easy. Those represented by −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 maleimide group having no radical polymerization property used in the above (Method 1) and (Method 1 ') will be described. Examples of the monomer (B) include acrylic monomers, aromatic vinyl monomers, vinyl ester monomers, and the like. Among these, an acrylic monomer is preferable. In this case, the radical polymerizable unsaturated group of the monomer (B) is a (meth) acryloyl group.

  The maleimide group having no radical polymerizability of the radically polymerizable unsaturated monomer (B) is the same as the compound (A) and the monomer (B) in the above (Method 1) or (Method 1 ′). As long as the carbon-carbon unsaturated double bond of the maleimide group does not participate in this copolymerization reaction, that is, does not have radical polymerizability in the copolymerization reaction, it can be used without particular limitation. A disubstituted maleimide group in which a substituent such as an alkyl group is bonded to carbon of a carbon-carbon unsaturated double bond represented by the following general formula (1) is preferable. By using such a radically polymerizable unsaturated monomer (B) having a disubstituted maleimide group, the double bond of the maleimide group is consumed in the copolymerization reaction when copolymerizing with the compound (A). The fluorine-containing curable resin (V1) or (V1 ′), which is the target product, can be obtained. The maleimide group is a functional group that can be photocured by causing a photodimerization reaction by irradiation with an active energy ray even in the absence of a photopolymerization initiator (H) described later.

（式中、Ｒ^１及びＲ^２は、それぞれ独立して、炭素原子数１〜６のアルキル基、又はＲ^１とＲ^２とが１つとなって５員環もしくは６員環を形成する炭化水素基を表す。）

(In the formula, R ¹ and R ² are each independently an alkyl group having 1 to 6 carbon atoms, or a hydrocarbon in which R ¹ and R ² are combined to form a 5-membered or 6-membered ring. Represents a group.)

  Specific examples of the maleimide group represented by the general formula (1) include the following formulas (1-1) to (1-3).

  Furthermore, specific examples of the monomer (B) include compounds represented by the following formulas (B-1) to (B-6).

  Next, the radically polymerizable unsaturated monomer (C) having a reactive functional group (c) 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 (C) include acrylic monomers, aromatic vinyl monomers, vinyl ester monomers, and the like. Among these, an acrylic monomer is preferable. In this case, the radical polymerizable unsaturated group of the monomer (B) is a (meth) acryloyl group.

  Here, examples of the reactive functional group (c) possessed by the radical polymerizable unsaturated monomer (C) include a hydroxyl group, an isocyanate group, an epoxy group, and a carboxyl group, and the radical polymerizable unsaturated monomer. Examples of the monomer (C) 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.

  Further, when the compound (A) and the monomer (B) are copolymerized in the (Method 1), or in the (Method 1 ′), the compound (A), the monomer (B) and When the monomer (C) is copolymerized, other radical polymerizable unsaturated monomers may be copolymerized. Examples of such other radical polymerizable unsaturated monomers include methyl (meth) acrylate, ethyl (meth) acrylate, (meth) acrylate-n-propyl, (meth) acrylate-n-butyl, (Meth) acrylic acid isobutyl, (meth) acrylic acid-n-pentyl, (meth) acrylic acid-n-hexyl, (meth) acrylic acid-n-heptyl, (meth) acrylic acid-n-octyl, (meth) 2-ethylhexyl acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopenta (meth) acrylate Nyl, (meth) acrylic acid esters such as (meth) acrylic acid dicyclopentenyl; styrene, α-methylstyrene, p- Aromatic vinyls such as tilstyrene and p-methoxystyrene; maleimide, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-butylmaleimide, N-hexylmaleimide, N-octylmaleimide, N-dodecylmaleimide, And maleimides such as N-stearylmaleimide, N-phenylmaleimide and N-cyclohexylmaleimide. These other monomers are also obtained in (Method 2) or (Method 2 ′) by copolymerizing the compound (A) and the monomer (C) to obtain a polymer (P2). In this case, it can be used similarly as a raw material for the polymer (P2).

  Here, when obtaining the fluorine-containing curable resin (V1) of the present invention in (Method 1), the polymer (P1) which is an intermediate product of the fluorine-containing curable resin of the present invention is obtained in (Method 1 ′). In (Method 2) and (Method 2 ′), when obtaining the polymer (P2) which is an intermediate product of the fluorine-containing curable resin of the present invention, the compound (A), the monomer (B) ), The monomer (C), and, if necessary, other radical polymerizable unsaturated monomers are polymerized 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.

  Functionality having reactivity with the reactive functional group (c) of the monomer (C) which is the raw material of the polymer (P1) is added to the polymer (P1) obtained in the above (Method 1 ′). The target fluorine-containing curable resin (V1 ′) can be obtained by reacting the compound (D) having the group (d) and the active energy ray-curable group. Further, the polymer (P2) obtained in the above (Method 2) has reactivity with the reactive functional group (c) of the monomer (C) which is a raw material of the polymer (P2). The target fluorine-containing curable resin (V2) is obtained by reacting the compound (E) having a functional group (e) and a maleimide group. Furthermore, the reactivity of the polymer (P2) obtained in the above (Method 2 ′) with the reactive functional group (c) of the monomer (C) that is the raw material of the polymer (P2) is increased. A compound (D) having a functional group (d) having an active energy ray-curable group, a compound (E) having a functional group (e) having reactivity with the functional group (c) and a maleimide group, Is reacted to obtain the intended fluorine-containing curable resin (V2 ′).

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

  As such a compound (D), specifically, the same compounds as those exemplified as the radical polymerizable unsaturated monomer (C) having the reactive functional group (c) can be used. Examples of those having two or more radical polymerizable groups include 2-hydroxy-3-acryloyloxypropyl methacrylate, pentaerythritol triacrylate, and dipentaerythritol pentaacrylate.

  Of these, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, 4-hydroxybutyl acrylate, 1,4- Cyclohexanedimethanol monoacrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, N- (2-hydroxyethyl) acrylamide, 2-acryloyloxyethyl isocyanate, 4-hydroxybutyl acrylate Glycidyl ether and acrylic acid are preferred.

  As the functional group (e) of the compound (E), the reactive functional group (c) of the monomer (C) is the same as the functional group (d) of the compound (D). Select according to the type. In particular, the reactive functional group (c) of the monomer (C) is an isocyanate group, and the functional group (e) of the compound (E) is a hydroxyl group, or the monomer ( It is preferable that the reactive functional group (c) possessed by C) is a hydroxyl group and the functional group (e) possessed by the compound (E) is an isocyanate group since the reaction proceeds smoothly.

  Moreover, as a maleimide group which the said compound (E) has, what is represented by following General formula (2) is mentioned, for example.

（式中、Ｒ^３及びＲ^４は、それぞれ独立して、水素原子もしくは炭素原子数１〜６のアルキル基、又はＲ^３とＲ^４とが１つとなって５員環もしくは６員環を形成する炭化水素基を表す。）

(Wherein R ³ and R ⁴ are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, or R ³ and R ⁴ are combined to form a 5-membered or 6-membered ring. Represents a hydrocarbon group.)

  Specific examples of the maleimide group represented by the general formula (2) include the following formulas (2-1) to (2-5).

  Furthermore, specific examples of the compound (E) include compounds represented by the following formulas (E-1) to (E-11).

  When the compound (D) is reacted with the polymer (P1) in the above (Method 1 ′), the above compound (E) is reacted with the polymer (P2) in the above (Method 2). In (Method 2 ′), the reaction conditions for reacting the compound (D) and the compound (E) with the polymer (P2) are the active energy ray-curable group and the compound (D) in the compound (D). The reaction may be performed under the condition that the maleimide group in E) is not polymerized. For example, the reaction is preferably carried out by adjusting the temperature condition in the 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 (c) is a hydroxyl group and the functional group (d) or the functional group (e) is an isocyanate group, or the functional group (c) is an isocyanate group, When the functional group (d) or the functional group (e) is a hydroxyl group, p-methoxyphenol, hydroquinone, 2,6-di-t-butyl-4-methylphenol or the like is used as a polymerization inhibitor and urethanized. A method in which dibutyltin dilaurate, dibutyltin diacetate, tin octylate, zinc octylate or the like is used as a reaction catalyst and the reaction is carried out at a reaction temperature of 40 to 120 ° C., particularly 60 to 90 ° C. is preferred. 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.

  Number of fluorine-containing curable resins (V1), (V1 ′), (V2) or (V2 ′) obtained by the above (Method 1), (Method 1 ′), (Method 2) or (Method 2 ′) The average molecular weight (Mn) is preferably in the range of 1,000 to 6,000, and more preferably in the range of 1,500 to 5,000. Further, the weight average molecular weight (Mw) is preferably in the range of 3,000 to 200,000, and more preferably in the range of 4,000 to 120,000. By setting Mn and Mw of the radical polymerizable resin (V) within these ranges, gelation during the production of the radical polymerizable resin (V) 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.

  In the fluorine-containing curable resin of the present invention, the fluorine content, which is the content ratio of fluorine atoms contained in the resin, is preferably from 2 to 35% by mass from the viewpoint of the antifouling property of the cured coating film.

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

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

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

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

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

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

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

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

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

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

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

  Examples of the active energy ray-curable monomer (G) 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 (G) 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 (F) and the active energy. It is preferably in the range of 0.01 to 10 parts by mass, more preferably in the range of 0.1 to 5% by mass, with respect to 100 parts by mass in total of the linear curable monomer (G). 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. Here, when the fluorine-containing curable resin of the present invention is used alone as a cured coating film, the fluorine-containing curable resin (V1) or (V2) obtained by the above (Method 1) or (Method 2) is active. Since it has only a maleimide group as an energy ray curable group, even if no photopolymerization initiator is present, photodimerization reaction of the maleimide group occurs by irradiation with active energy rays, and photocuring is possible. On the other hand, when the fluorine-containing curable resin (V1 ′) or (V2 ′) obtained by the above (Method 1 ′) or (Method 2 ′) is used alone as a cured coating film, or the fluorine-containing curable resin of the present invention. When an active energy ray-curable coating composition containing a resin is irradiated with ultraviolet rays as an active energy ray to form a cured coating film, photopolymerization is carried out in the fluorine-containing curable resin or active energy ray-curable composition. It is preferable to add an initiator (H) to improve curability. 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 H) or a photosensitizer.

  Examples of the photopolymerization initiator (H) 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 (H), the compatibility with the active energy ray-curable resin (F) and the active energy ray-curable monomer (G) 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 (H) can be used alone or in combination of two or more.

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

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

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

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

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

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

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

  The application method of the active energy ray-curable coating composition of the present invention varies depending on the application. Examples thereof include a coating method using a coater, dipping, screen printing, spray, applicator, bar coater, etc., or a molding method using various molds.

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

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

  Further, as a coating material that can improve the leveling property by adding the fluorine-containing curable resin of the present invention and impart antifouling properties (ink repellency, fingerprint resistance, etc.) to the coating film, an LCD such as a TAC film can be used. Hard coating materials for protective films for polarizing plates, anti-glare (AG: anti-glare) coating materials or anti-reflection (LR) coating materials; hard coating materials for various display screens such as plasma displays and organic EL displays (PDP); for touch panels Hard coating material; 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 (PD ), Resin composition for pixel partition walls such as organic EL display; paint for mobile phone casing or hard coat material; hard coat material for screen of mobile phone; hard coat material for optical recording medium such as CD, DVD, Blu-ray disc; Hard coating material for transfer film for insert molds (IMD, IMF); Coating material for rubber rollers 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, videos Coating materials for optical lenses such as cameras and glasses; windshields for watches such as watches; coating materials for glass; coating materials for windows of various vehicles such as automobiles and railway vehicles; printing inks or paints for various building materials such as decorative panels; Window glass coating materials; wood coatings for furniture, etc .; coating materials for artificial and synthetic leather; various plastics such as housings for home appliances Shaped piece 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 properties can be imparted.

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

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

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

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

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

[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]
Apparatus: “AL-400” manufactured by JEOL Ltd.
Solvent: acetone-d ₆

[GPC measurement conditions]
Measuring device: “HLC-8220 GPC” manufactured by Tosoh Corporation
Column: Guard column “HHR-H” manufactured by Tosoh Corporation (6.0 mm ID × 4 cm)
+ "TSK-GEL GMHHR" (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, and stirring was started in an air stream, and 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
91.1 parts by mass of methyl isobutyl ketone as a solvent was added to a glass flask equipped with a stirrer, a thermometer, a condenser, and a dropping device, and the temperature was raised to 105 ° C. while stirring in a nitrogen stream. Subsequently, 20 parts by mass (Drip 1) of (A-1-1) obtained in Synthesis Example 1, 19.2 parts by mass of 2-hydroxyethyl methacrylate, and N-acryloyloxyethyl tetrahydrophthalimide (formula (B- The compound represented by 5)) 211.3 parts by mass of monomer solution (drip liquid 2) in which 40 parts by mass of methyl isobutyl ketone was dissolved in 152.1 parts by mass and a radical polymerization initiator (t-butylperoxy-2-ethyl) Hexanoate) 3 types of dripping liquid and 42 parts by mass of radical polymerization initiator solution (drip liquid 3) in which 11.9 parts by mass of methyl isobutyl ketone was dissolved in 30.1 parts by mass were set in separate dripping apparatuses. While keeping the inside of the flask at 105 ° C., it was dropped simultaneously over 2 hours. After completion of dropping, the mixture was stirred at 105 ° C. for 10 hours, and then the solvent was distilled off under reduced pressure to obtain a polymer (P1-1).

Next, 101.2 parts by mass of methyl ethyl ketone as a solvent, 0.1 part by mass of p-methoxyphenol as a polymerization inhibitor, and 0.03 part by mass of tin octylate as a urethanization catalyst were added to the polymer (P1-1) obtained above. Then, stirring was started under an air stream, and 20.8 parts by mass of 2-acryloyloxyethyl isocyanate was added dropwise over 1 hour while maintaining 60 ° C. After completion of the dropwise addition, the mixture was stirred at 60 ° C. for 2 hours, then heated to 80 ° C. and stirred for 4 hours. As a result, the disappearance of the isocyanate group absorption peak was confirmed by IR spectrum measurement of the reaction solution. . Subsequently, methyl ethyl ketone was added as a solvent to obtain a methyl ethyl ketone solution containing 40% by mass of the fluorinated curable resin (1). As a result of measuring the molecular weight of the fluorine-containing curable resin (1) by GPC (polystyrene equivalent molecular weight), the number average molecular weight was 3,000 and the weight average molecular weight was 13,600. The fluorine content was 11% by mass. FIG. 1 shows an IR spectrum chart of the obtained fluorinated curable resin (1), FIG. 2 shows a ¹³ C-NMR chart, and FIG. 3 shows a GPC chart.

(Example 2)
69.3 parts by mass of methyl isobutyl ketone as a solvent was added to a glass flask equipped with a stirrer, a thermometer, a condenser, and a dropping device, and the temperature was raised to 105 ° C. while stirring under a nitrogen stream. Subsequently, 20.5 parts by mass (Drip 1) obtained in Synthesis Example 1 and 28.3 parts by mass of 2-hydroxyethyl methacrylate and N-acryloyloxyethyl tetrahydrophthalimide (the above formula ( Compound represented by B-5): 172.2 parts by mass of monomer solution (2 drops) dissolved in 123.4 parts by mass of methyl isobutyl ketone and 2 radical polymerization initiator (t-butylperoxy) 2-ethylhexanoate) 3 types of dripping liquids separately with 25.5 parts by mass of radical polymerization initiator solution (drip liquid 3) in which 10.4 parts by mass of methyl isobutyl ketone was dissolved in 15.1 parts by mass 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, and then the solvent was distilled off under reduced pressure to obtain a polymer (P1-2).

  Next, 101.0 parts by mass of methyl ethyl ketone as a solvent, 0.1 part by mass of p-methoxyphenol as a polymerization inhibitor, and 0.03 part by mass of tin octylate as a urethanization catalyst were added to the polymer (P1-2) obtained above. Then, stirring was started under an air stream, and 30.7 parts by mass of 2-acryloyloxyethyl isocyanate was added dropwise over 1 hour while maintaining 60 ° C. After completion of the dropwise addition, the mixture was stirred at 60 ° C. for 2 hours, then heated to 80 ° C. and stirred for 4 hours. As a result, the disappearance of the isocyanate group absorption peak was confirmed by IR spectrum measurement of the reaction solution. . Subsequently, methyl ethyl ketone was added as a solvent to obtain a methyl ethyl ketone solution containing 40% by mass of the fluorinated curable resin (2). As a result of measuring the molecular weight of this fluorine-containing curable resin (2) by GPC (polystyrene conversion molecular weight), it was a number average molecular weight 2,700 and a weight average molecular weight 9,200. The fluorine content was 11% by mass.

(Example 3)
70.9 parts by mass of methyl isobutyl ketone was added as a solvent to a glass flask equipped with a stirrer, thermometer, condenser, and dropping device, and the temperature was raised to 95 ° C. while stirring under a nitrogen stream. Next, 20 parts by mass (Drip 1) obtained in Synthesis Example 1, 44 parts by mass of 2-methacryloyloxyethyl isocyanate (Drip 2), and a radical polymerization initiator (2, 2). Three types of dropwise addition with 57.5 parts by weight of a radical polymerization initiator solution (dropping liquid 3) in which 9.6 parts by weight of '-azobis (2-methylbutyronitrile)) was dissolved in 47.9 parts by weight 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 95 ° C. After completion of dropping, the solution was stirred at 95 ° C. for 10 hours to obtain a polymer (P2-1) solution.

  Next, 21.2 parts by mass of methyl ethyl ketone as a solvent, 0.1 part by mass of p-methoxyphenol as a polymerization inhibitor, and tin octylate as a urethanization catalyst were added to the polymer (P2-1) solution obtained above. 03 parts by mass was added, and 36 parts by mass of N-hydroxyethylcitraconimide (compound represented by the above formula (E-2)) was added in four portions while stirring at an air flow and maintaining 60 ° C. . Then, after stirring at 60 ° C. for 2 hours, the reaction was carried out by raising the temperature to 80 ° C. and stirring for 4 hours. As a result, disappearance of the absorption peak of the isocyanate group was confirmed by IR spectrum measurement of the reaction solution. By this operation, a methyl isobutyl ketone / methyl ethyl ketone solution containing 40% by mass of the fluorinated curable resin (3) was obtained. As a result of measuring the molecular weight of this fluorine-containing curable resin (3) by GPC (polystyrene conversion molecular weight), it was a number average molecular weight 2,100 and a weight average molecular weight 26,000. The fluorine content was 11% by mass.

Example 4
69.3 parts by mass of methyl isobutyl ketone as a solvent was added to a glass flask equipped with a stirrer, a thermometer, a condenser, and a dropping device, and the temperature was raised to 95 ° C. while stirring under a nitrogen stream. Subsequently, 20.4 parts by mass (drop 1) of (A-1-1) obtained in Synthesis Example 1, 43.5 parts by mass of 2-methacryloyloxyethyl isocyanate (drop 2), and a radical polymerization initiator. With 58.1 parts by mass (dropping solution 3) of radical polymerization initiator solution in which 9.6 parts by mass of (2,2′-azobis (2-methylbutyronitrile)) was dissolved in 48.5 parts by mass of methyl isobutyl ketone Three types of dropping liquids were set in separate dropping apparatuses, respectively, and dropped simultaneously over 2 hours while maintaining the inside of the flask at 95 ° C. After completion of dropping, the solution was stirred at 95 ° C. for 10 hours to obtain a polymer (P2-2) solution.

  Next, 0.1 parts by mass of p-methoxyphenol as a polymerization inhibitor and 0.03 parts by mass of tin octylate as a urethanization catalyst were added to the polymer (P2-2) solution obtained above, 19.8 parts by weight of N-hydroxyethylmaleimide (compound represented by the above formula (E-1)) and 16.3 parts by weight of 2-hydroxyethyl acrylate were added to methyl ethyl ketone 22.5 while stirring at 60 ° C. The solution dissolved in parts by mass was added in four portions. Then, after stirring at 60 ° C. for 2 hours, the reaction was carried out by raising the temperature to 80 ° C. and stirring for 4 hours. As a result, disappearance of the absorption peak of the isocyanate group was confirmed by IR spectrum measurement of the reaction solution. By this operation, a methyl isobutyl ketone / methyl ethyl ketone solution containing 40% by mass of the fluorinated curable resin (4) was obtained. As a result of measuring the molecular weight of this fluorine-containing curable resin (4) by GPC (polystyrene conversion molecular weight), it was number average molecular weight 3,900 and weight average molecular weight 105,000. The fluorine content was 11% by mass.

(Example 5)
79.2 parts of methyl isobutyl ketone was added as a solvent to a glass flask equipped with a stirrer, thermometer, condenser, and dropping device, and the temperature was raised to 105 ° C. while stirring under a nitrogen stream. Subsequently, 20 parts by mass (Drip 1) obtained in Synthesis Example 1, 38.7 parts by mass of glycidyl methacrylate (Drip 2), and a radical polymerization initiator (t-butylperoxy- 2-ethylhexanoate) 3.8 parts by mass of a radical polymerization initiator solution obtained by dissolving 8.8 parts by mass of methyl isobutyl ketone in 16.2 parts (drip liquid 3) was added to separate dropping devices. The flask was added dropwise at the same time over 2 hours while keeping the inside of the flask at 105 ° C. After completion of dropping, the solution was stirred at 105 ° C. for 10 hours to obtain a polymer (P2-3) solution.

  Next, 0.1 part of p-methoxyphenol as a polymerization inhibitor and 0.1 part of a 50% by weight aqueous solution of tetramethylammonium chloride as a catalyst were added to the polymer (P2-3) solution obtained above, and an air stream Under stirring and heating, when 60 ° C. is reached, 20.6 parts by mass of maleimidoacetic acid (compound represented by the formula (E-8)) and 9.6 parts by mass of acrylic acid are added to methyl isobutyl ketone. A solution dissolved in 21.3 parts by mass was added. Thereafter, the temperature was further increased until reaching 100 ° C., and the reaction was carried out by stirring at 100 ° C. for 13 hours. As a result, the disappearance of the carbonyl group was confirmed by measuring the acid value of the reaction solution. By this operation, a methyl isobutyl ketone solution containing 43% by mass of the fluorinated curable resin (5) was obtained. As a result of measuring the molecular weight of this fluorine-containing curable resin (5) by GPC (polystyrene conversion molecular weight), it was number average molecular weight 2,200 and weight average molecular weight 9,100. The fluorine content was 11% by mass.

  For the fluorine-containing curable resins (1) to (5) synthesized in Examples 1 to 5, raw materials, molecular weights, and the like are summarized in Table 1.

The abbreviations in Table 1 are as follows.
HEA: 2-hydroxyethyl acrylate HEMA: 2-hydroxyethyl methacrylate AOI: 2-acryloyloxyethyl isocyanate MOI: 2-methacryloyloxyethyl isocyanate GMA: glycidyl methacrylate AA: acrylic acid

(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 a polymer solution.

  Next, 0.1 parts by mass of p-methoxyphenol as a polymerization inhibitor and 0.05 part 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. Next, a part of the solvent was distilled off under reduced pressure to obtain a methyl isobutyl ketone solution containing 50% by mass of the fluorinated curable resin (Z-1). The molecular weight of the fluorine-containing curable resin (Z-1) was measured by GPC (polystyrene equivalent molecular weight). As a result, the number average molecular weight was 3,000 and the weight average molecular weight was 7,000.

(Comparative Example 2)
Methyl isobutyl ketone 63 parts by mass was added as a solvent to a glass flask equipped with a stirrer, thermometer, condenser, and dropping device, and the temperature was raised to 105 ° C. while stirring under a nitrogen stream. Then, 21.5 parts by mass (Drip 1) obtained in Synthesis Example 1, 41.3 parts by mass of 2-hydroxyethyl methacrylate (Drip 2), and a radical polymerization initiator ( (t-butylperoxy-2-ethylhexanoate) 9.4 parts by mass of radical polymerization initiator solution 135.4 parts by mass of methyl isobutyl ketone 126 parts by mass (Drips 3) Each was set in a separate dropping device 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, and then the solvent was distilled off under reduced pressure to obtain a polymer.

  Next, 74.7 parts by mass of methyl ethyl ketone as a solvent, 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 are added to the polymer obtained above, and air is added. 44.8 parts by mass of 2-acryloyloxyethyl isocyanate was added dropwise over 1 hour while stirring at an air flow and maintaining 60 ° C. After completion of the dropwise addition, the mixture was stirred at 60 ° C. for 1 hour, then heated to 80 ° C. and stirred for 5 hours. As a result, the disappearance of the isocyanate group absorption peak was confirmed by IR spectrum measurement of the reaction solution. . Next, methyl ethyl ketone was added as a solvent to obtain a methyl ethyl ketone solution containing 50% by mass of the fluorinated curable resin (Z-2). As a result of measuring the molecular weight of this fluorine-containing curable resin (Z-2) by GPC (polystyrene conversion molecular weight), it was number average molecular weight 2,400 and weight average molecular weight 7,100.

(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.

(Examples 6 to 10, Comparative Examples 3 to 5)
To the 268 parts by mass of the base resin composition obtained above, uniformly add 1 part by mass of the fluorine-containing curable resin solutions obtained in Examples 1 to 5 and Comparative Examples 1 and 2 as a resin component. By mixing, an active energy ray-curable coating composition was obtained. Next, this active energy ray-curable coating composition was applied to a bar coater No. Example 6 was applied to a PET film having a thickness of 188 μm, and then put in a drier at 60 ° C. for 5 minutes to evaporate the solvent, and cured by irradiating with ultraviolet rays (UV) with an ultraviolet curing device. -10 and Comparative Examples 3 to 4 were prepared as coated films. The irradiation conditions of ultraviolet rays were as follows: (1) use of a high-pressure mercury lamp in a nitrogen atmosphere, ultraviolet irradiation amount of ² kJ / m ² , and (2) use of a high-pressure mercury lamp in an air (oxygen concentration of 21%) atmosphere. Two levels of 5 kJ / m ² were set. Moreover, the coating film was similarly produced about the active energy ray hardening-type coating composition in which nothing was added, and it was set as the comparative example 5.

  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.

  The evaluation results are shown in Table 2.

  The cured coating film of the active energy ray-curable coating composition of Examples 6 to 10 to which the fluorine-containing curable resin obtained in Examples 1 to 5 which is the fluorine-containing curable resin of the present invention is added is in a nitrogen atmosphere. It was found that in the UV curing in the above, it has excellent anti-smudge property and stain wiping property. Furthermore, it has been found that UV curing under an air atmosphere (in the presence of oxygen) has excellent dirt adhesion prevention and dirt wiping properties equivalent to those when UV curing is performed under a nitrogen atmosphere.

  On the other hand, in Comparative Examples 3 and 4 using the fluorinated curable resins (Z-1) and (Z-2), the UV curing under a nitrogen atmosphere showed good antifouling property, In Example 3, the dirt wiping property was insufficient. Further, in UV curing under an air atmosphere, both Comparative Examples 3 and 4 had relatively good anti-smudge properties, but the stain wiping property was insufficient. In addition, Comparative Example 5 in which nothing was added was UV curing under a nitrogen atmosphere and an air atmosphere, and both the stain adhesion preventing property and the stain wiping property were poor.

Claims (14)

The resin structure a fluorine-containing curable resin that having a poly (perfluoroalkylene ether) chain and a maleimide group, the fluorine-containing curable resin is poly (perfluoroalkylene ether) chain and radical-polymerizable at both ends Obtained by copolymerizing a compound (A) having a structural moiety having an unsaturated group and a radically polymerizable unsaturated monomer (B) having a maleimide group having no radical polymerizability as essential monomer components. A fluorine-containing curable resin characterized by being a radically polymerizable resin.   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 maleimide group having no radically polymerizable property ( B) and a radically polymerizable unsaturated monomer (C) having a reactive functional group (c) are copolymerized as essential monomer components to a polymer (P1), and the functional group ( The fluorine-containing curable resin according to claim 1, which is obtained by reacting a compound (D) having a functional group (d) having reactivity with c) and an active energy ray-curable group. The reactive functional group (c) of the radical polymerizable unsaturated monomer (C) is an isocyanate group and the functional group (d) of the compound (D) is a hydroxyl group, or the radical The fluorine-containing curing according to claim 2 , wherein the reactive functional group (c) of the polymerizable unsaturated monomer (C) is a hydroxyl group, and the functional group (d) of the compound (D) is an isocyanate group. Resin. The fluorine-containing fluorine according to any one of claims 1 to 3, wherein the radical-polymerizable unsaturated monomer (B) has a maleimide group having no radical polymerizability, which is a maleimide group represented by the following general formula (1). Curable resin.

(In the formula, R ¹ and R ² are each independently an alkyl group having 1 to 6 carbon atoms, or a hydrocarbon in which R ¹ and R ² are combined to form a 5-membered or 6-membered ring. Represents a group.) A fluorine-containing curable resin having a poly (perfluoroalkylene ether) chain and a maleimide group in the resin structure, and the fluorine-containing curable resin is a radically polymerizable unsaturated group at the poly (perfluoroalkylene ether) chain and both ends thereof. Polymer obtained by copolymerizing compound (A) having structural group having group and radical polymerizable unsaturated monomer (C) having reactive functional group (c) as essential monomer components to (P2), the functional groups (c) and the fluorine-containing curable resin compound having a functional group (e) and a maleimide group reactive with the (E) are reacted, characterized in that it is obtained by the. 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 (c) (C ) As an essential monomer component, the polymer (P2) has a functional group (d) having reactivity with the functional group (c) and an active energy ray-curable group. 6. The fluorine-containing compound according to claim 5 , wherein the compound (D) is obtained by reacting a compound (E) having a maleimide group with a functional group (e) having reactivity with the functional group (c). Curable resin. The reactive functional group (c) of the radical polymerizable unsaturated monomer (C) is an isocyanate group and the functional group (e) of the compound (E) is a hydroxyl group, or the radical reactive functional groups polymerizable unsaturated monomer (C) has (c) is a hydroxyl group, and containing the compound (E) according to claim 5 or 6, wherein the functional group (e) is an isocyanate group of the Fluorine curable resin. The reactive functional group (c) of the radical polymerizable unsaturated monomer (C) is an isocyanate group, and the functional group (d) of the compound (D) and the functional group of the compound (E). (E) is a hydroxyl group, or the reactive functional group (c) of the radical polymerizable unsaturated monomer (C) is a hydroxyl group and the functional group (d) of the compound (D) and the compound (E) a functional group having the (e) is a fluorine-containing curable resin according to claim 6 wherein the isocyanate groups. The fluorine-containing curable resin according to any one of claims 5 to 8 , wherein the maleimide group of the compound (E) is a maleimide group represented by the following general formula (1).

(Wherein R ³ and R ⁴ are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, or R ³ and R ⁴ are combined to form a 5-membered or 6-membered ring. Represents a hydrocarbon group.) The fluorine-containing curable resin according to any one of claims 1 to 9 , 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 10 to a base material and irradiating and curing the active energy ray. An activity comprising the fluorine-containing curable resin according to any one of claims 1 to 10 , and the active energy ray curable resin (F) or the active energy ray curable monomer (G). Energy ray curable coating composition. The active energy ray-curable coating composition according to claim 12 , wherein the fluorine-containing curable resin according to any one of claims 1 to 10 is used as a fluorine-based surfactant or a fluorine-based surface modifier. A cured product obtained by applying the active energy ray-curable coating composition according to claim 12 or 13 to a substrate and irradiating and curing the active energy ray.

Images