JP2011074248A - Fluorine-containing curable resin, active energy beam curable type coating composition, and cured article of the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide: a fluorine-containing curable resin capable of imparting an excellent anti-fouling property on a cured coated film surface, and being used as a fluorine-based surfactant and fluorine-based surface-modifying agent; an active energy beam-curable type coating composition capable of improving the stability of surface functions such as the anti-fouling property, etc.; and a cured article of the same. <P>SOLUTION: The fluorine-containing curable resin is characterized in that it is a radically polymerizable resin (I) obtained by introducing ≥2 radically polymerizable unsaturated groups per 1 molecule of a monomer (B) by utilizing a reactive functional group (b) of the monomer (B) to a polymer (P) obtained by copolymerizing, as essential monomer components, a compound (A) having structural sites having a poly(perfluoroalkylene ether) chain and radically polymerizable unsaturated groups at both terminals of the same and the radically polymerizable unsaturated monomer (B) having the reactive functional group (b). <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 that can impart excellent antifouling properties to the surface of a cured coating film and can be used as a fluorine-based surfactant. In addition, it is possible to prevent volatilization or desorption of the fluorosurfactant or its decomposition product from the coating film surface after coating and curing, 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 found that a monomer having a poly (perfluoroalkylene ether) chain and a functional group capable of introducing a radically polymerizable unsaturated group later. A fluorine-containing curable resin in which two or more radically polymerizable unsaturated groups are introduced per molecule of the latter monomer into the copolymer. What is blended in the active energy ray curable coating composition as a surfactant can suppress volatilization and detachment of the fluorinated curable resin or its decomposition product from the cured coating film, and has antifouling properties on the coating film surface. The present inventors have found that surface performance can be stably imparted and completed the present invention.

  That is, the present invention relates to a compound (A) having a poly (perfluoroalkylene ether) chain and a structural site having a radically polymerizable unsaturated group at both ends thereof, and a radically polymerizable group having a reactive functional group (b). Using the reactive functional group (b) of the monomer (B) to the polymer (P) obtained by copolymerizing the saturated monomer (B) as an essential monomer component, The present invention provides a fluorine-containing curable resin, which is the radically polymerizable resin (I) into which two or more radically polymerizable unsaturated groups are introduced per molecule of the monomer (B).

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

  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.

FIG. 1 is an IR spectrum chart of the radical polymerizable resin (I1) obtained in Example 1. FIG. 2 is a ¹³ C-NMR chart of the radical polymerizable resin (I1) obtained in Example 1. FIG. 3 is an IR spectrum chart of the radical polymerizable resin (I2) obtained in Example 2. FIG. 4 is a ¹³ C-NMR chart of the radical polymerizable resin (I2) obtained in Example 2. FIG. 5 is an IR spectrum chart of the radical polymerizable resin (I3) obtained in Example 3. FIG. 6 is a ¹³ C-NMR chart of the radical polymerizable resin (I3) obtained in Example 3. FIG. 7 is an IR spectrum chart of the radical polymerizable resin (I4) obtained in Example 4. FIG. 8 is a ¹³ C-NMR chart of the radical polymerizable resin (I4) obtained in Example 4. FIG. 9 is an IR spectrum chart of the radical polymerizable resin (I5) obtained in Example 5. FIG. 10 is a ¹³ C-NMR chart of the radical polymerizable resin (I5) obtained in Example 5.

  The fluorine-containing curable resin of the present invention has a poly (perfluoroalkylene ether) chain, a compound (A) having a structural moiety having a radical polymerizable unsaturated group at both ends thereof, and a reactive functional group (b). The reactive functional group (b) of the monomer (B) is added to the polymer (P) obtained by copolymerizing the radical polymerizable unsaturated monomer (B) as an essential monomer component. It is a fluorine-containing curable resin characterized by being a radically polymerizable resin (I) in which two or more radically polymerizable unsaturated groups are introduced per molecule of the monomer (B). This fluorine-containing curable resin can be obtained by, for example, 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 ) As an essential monomer component, a functional group (c) having reactivity with the functional group (b) and two or more radical polymerizable unsaturated groups. The compound (C) which has these is made to react, and a fluorine-containing curable resin is obtained as a radically polymerizable resin. The radical polymerizable resin obtained by this method is referred to as “radical polymerizable resin (I-1)”.

(Method 2)
Radical polymerizability having a poly (perfluoroalkylene ether) chain and a compound (A) having a structural moiety having a radically polymerizable unsaturated group at both ends and a cyclic ether group (b ′) capable of undergoing a ring-opening addition reaction A functional group (P ′) obtained by copolymerizing an unsaturated monomer (B ′) as an essential monomer component with addition reactivity to the cyclic ether group (b ′) ( c ′) and a compound (C ′) having a radically polymerizable unsaturated group are reacted, and then an isocyanate group or a carboxylic acid halide group and a radically polymerizable unsaturated group are added to the hydroxyl group produced by the reaction. A method of obtaining a fluorine-containing curable resin as a radically polymerizable resin by reacting a compound (D) having The radical polymerizable resin obtained by this method is referred to as “radical polymerizable resin (I-2)”.

  First, (Method 1) for obtaining the radical polymerizable resin (I-1) will be described. The poly (perfluoroalkylene ether) chain used in this method and the poly (perfluoroalkylene ether) chain possessed by the compound (A) having a structural moiety having a radically polymerizable unsaturated group at both ends thereof have 1 carbon atom. And those having a structure in which a divalent fluorocarbon group of ~ 3 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.

  Next, the radically polymerizable unsaturated group possessed at both ends of the chain of the compound (A) is represented by the following structural formulas U-1 to U-4 at both ends of the poly (perfluoroalkylene ether) chain. Those having a radically polymerizable unsaturated group represented by the formula:

  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 described above 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-5 are particularly preferable because the industrial production of the compound (A) itself is easy and the polymerization reaction for producing the polymer (P1) is also easy. Are preferred.

  In order to produce the above compound (A), for example, a method obtained by dehydrochlorinating (meth) acrylic acid chloride to a perfluoropolyether having one hydroxyl group at both ends, (meth) acrylic acid A method obtained by dehydration reaction, a method obtained by urethanation of 2- (meth) acryloyloxyethyl isocyanate, a method obtained by esterification of itaconic anhydride, perfluoro having one carboxyl group at both ends For a polyether, a method obtained by esterifying 4-hydroxybutyl acrylate glycidyl ether, a method obtained by esterifying glycidyl methacrylate, and a perfluoropolyether having one isocyanate group at both ends. , 2-hydroxyethylacrylamide reaction method And the like. Among these, a method obtained by dehydrochlorinating (meth) acrylic acid chloride to perfluoropolyether having one hydroxyl group at both ends, and urethanization of 2- (meth) acryloyloxyethyl isocyanate The method obtained by reacting is particularly preferable in that it can be 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.

  Further, as the radical polymerizable unsaturated monomer (B) having a reactive functional group (b) used in (Method 1), an acrylic monomer, an aromatic vinyl monomer, a vinyl ester monomer Body, maleimide monomers and the like. In the present invention, since it is necessary to introduce a radical polymerizable unsaturated group into the side chain of the polymer of the radical polymerizable unsaturated monomer (B), a reactive functional group is added to a part or all of the monomer component. Those having (b) are 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- (meth) Isocyanate group-containing unsaturated monomers such as acryloyloxyethyl isocyanate, 2- (2- (meth) acryloyloxyethoxy) ethyl isocyanate, 1,1-bis ((meth) acryloyloxymethyl) ethyl isocyanate; glycidyl methacrylate, 4 -Epoxy group-containing unsaturated monomers such as hydroxybutyl acrylate glycidyl ether; (meth) acrylic acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethylphthalic acid, maleic acid, itacon Carboxyl group-containing unsaturated monomer and the like; 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 methacrylate; styrene, α-methylstyrene, p-methylstyrene, p-methoxystyrene Aromatic vinyls; maleimide, methyl maleimide, ethyl maleimide, propyl maleimide, butyl maleimide, hexyl maleimide, octyl maleimide, dodecyl maleimide, stearyl maleimide, phenyl maleimide, maleimide such as cyclohexyl maleimide.

  Here, the method for producing the polymer (P) of (Method 1) includes the compound (A), the radically polymerizable unsaturated monomer (B) having a reactive functional group (b), and further necessary. Can be used to polymerize other radical polymerizable unsaturated monomers 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) needs to be within 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) has a number average molecular weight (Mn) of 800 to 3,000 in that the number of polymerizable unsaturated groups in one molecule of the finally obtained radical polymerizable resin increases. In particular, it is preferably in the range of 1,000 to 2,500, and the weight average molecular weight (Mw) is preferably in the range of 1,500 to 40,000, particularly 2,000 to 30,000.

  The polymer (P) obtained as described above is reacted with the compound (C) having a functional group (c) having reactivity with the functional group (b) and two or more radically polymerizable unsaturated groups. By making it, the target radically polymerizable resin (I-1) is obtained.

  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.

  The compound (C) is not particularly limited as long as it has the functional group (c) and two or more radically polymerizable unsaturated groups. For example, pentaerythritol tri (meth) acrylate , Dimethylolpropane tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, bis (2- (meth) acryloyloxyethyl) hydroxyethyl isocyanurate, 2-hydroxy-3-acryloyloxypropyl methacrylate, 2-hydroxy- Examples include 3-allyloxypropyl acrylate and 1,1-bis ((meth) acryloyloxymethyl) ethyl isocyanate. Among these, acrylates are preferred because of their high polymerization curability under ultraviolet irradiation.

  A method of reacting the polymer (P) with a compound (C) containing a functional group (c) reactive with the functional group (b) and two or more radically polymerizable unsaturated groups is a compound. The reaction may be carried out under conditions in which the radically polymerizable unsaturated group in (C) is not polymerized. 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.

  Examples of the radical polymerizable unsaturated monomer (B ′) having a cyclic ether group (b ′) capable of undergoing the ring-opening addition reaction used in (Method 2) include acrylic monomers and aromatic vinyl monomers. , Vinyl ester monomers, maleimide monomers, and the like. If the cyclic ether group (b ′) and the radical polymerizable unsaturated group are used, the monomer (B ′) is used. be able to. Moreover, examples of the cyclic ether group (b ′) of the monomer (B ′) include an epoxy group, an oxetanyl group, and a tetrahydrofurfuryl group.

  Specific examples of the monomer (B ′) include, for example, glycidyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, 3-methyl-3-oxetanyl (meth) acrylate, and 3-ethyl-3. -Oxetanyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, caprolactone-modified tetrahydrofurfuryl (meth) acrylate and the like. Among these, glycidyl methacrylate is preferable because of good reactivity.

  In (Method 2), the compound (A) and the monomer (B ′) are copolymerized to obtain a polymer (P ′). This copolymerization method is the same as in (Method 1). It can be carried out. Moreover, you may copolymerize using another radically polymerizable unsaturated monomer similarly to (Method 1).

  The molecular weight of the obtained polymer (P ′) needs to be within 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 ′) 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. 000, particularly 1,000 to 2,500, and the weight average molecular weight (Mw) is preferably 1,500 to 40,000, particularly 2,000 to 30,000. .

  First, a compound having a functional group (c ′) having an addition reactivity to the cyclic ether group (b ′) and a radically polymerizable unsaturated group (P ′) obtained as described above (P ′) C ′) is reacted, and the secondary radical produced by this reaction is reacted with a compound (D) having an isocyanate group or a carboxylic acid halide group and a radically polymerizable unsaturated group, thereby producing a target radical. A polymerizable resin (I-2) is obtained. In addition, when making the said compound (C ') react with the said cyclic ether group (b'), reaction can also be promoted using an acid catalyst etc.

  Examples of the functional group (c ′) of the compound (C ′) include a carboxyl group and a hydroxyl group. Specific examples of the compound (C ′) include (meth) acrylic acid, 2- (meth) acryloyloxyethyl phthalate, 2- (meth) acryloyloxypropyl phthalate, 2-hydroxyethyl (meth) acrylate, 2 -Hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-cyclohexanoloxy-2-ethyl (meth) acrylate, 2- (meth) acryloyloxyethyl-2 -Hydroxyethyl phthalate, 2-hydroxy-1-octyloxypropyl acrylate, 2-hydroxy-1-pentadecyloxypropyl acrylate, pentaerythritol tri (meth) acrylate, dimethylolpropane tri (meth) acrylate , Dipentaerythritol penta (meth) acrylate, bis (2- (meth) acryloyloxyethyl) hydroxyethyl isocyanurate, 2-hydroxy-3-acryloyloxypropyl methacrylate, 2-hydroxy-3-allyloxypropyl acrylate, etc. It is done. Among these, acrylic acid is preferable because of its good reactivity and curability with the cyclic ether group (b ′).

  In the reaction of the polymer (P ′) and the compound (C ′), when the functional group (c ′) is a carboxyl group, p-methoxyphenol, hydroquinone, 2,6-di- t-butyl-4-methylphenol and the like, tertiary amines such as triethylamine as an esterification reaction catalyst, quaternary ammoniums such as tetramethylammonium chloride, tertiary phosphines such as triphenylphosphine, It is preferable to use a quaternary phosphonium compound such as tetrabutylphosphonium chloride and react at a reaction temperature of 80 to 130 ° C., particularly 100 to 120 ° C. The organic solvent used in this reaction can be the same as described in (Method 1).

  Examples of the compound (D) include 2- (meth) acryloyloxyethyl isocyanate, 2- (2- (meth) acryloyloxyethoxy) ethyl isocyanate, 1,1-bis ((meth) acryloyloxymethyl) ethyl isocyanate. A compound having an isocyanate group and a radically polymerizable unsaturated group, such as a compound having a carboxylic acid halide group and a radically polymerizable unsaturated group such as (meth) acrylic acid chloride and (meth) acrylic acid bromide, etc. .

  When the functional group of the compound (D) is an isocyanate group, p-methoxyphenol, hydroquinone, 2,6-di-t-butyl-4-methylphenol or the like is used as a polymerization inhibitor, and a urethanization reaction catalyst A method of using dibutyltin dilaurate, dibutyltin diacetate, tin octylate, zinc octylate and the like at a reaction temperature of 40 to 120 ° C., particularly 60 to 90 ° C. is preferable. The organic solvent used in this reaction can be the same as described in (Method 1).

  As a method for obtaining the radical polymerizable resin (I) other than the above (Method 1) and (Method 2), as the radical polymerizable unsaturated monomer (B), maleic acid, itaconic acid or an anhydride thereof is used. In the case where an acid anhydride is used, a polymer is obtained by copolymerizing with the compound (A), and further reacted with water, so that two carboxyl groups per molecule of the monomer (B) After the introduction, by reacting these carboxyl groups with a compound having an epoxy group and a radically polymerizable unsaturated group, two radically polymerizable unsaturated groups per molecule of the monomer (B) are obtained. A method for obtaining the introduced radical polymerizable resin (I) is mentioned.

  Furthermore, after obtaining the above-mentioned radical polymerizable resin (I), an isocyanate group or a carboxylic acid halide group and a radical are produced in the same manner as in (Method 2) with respect to the hydroxyl group produced by the ring-opening addition reaction of the epoxy group. There is also a method for obtaining a radical polymerizable resin (I) in which four radical polymerizable unsaturated groups are introduced per molecule of the monomer (B) by reacting a compound (D) having a polymerizable unsaturated group. Can be mentioned.

  Further, as the radical polymerizable unsaturated monomer (B), an acid anhydride such as maleic anhydride or itaconic anhydride is used to copolymerize with the compound (A) to obtain a polymer. By reacting a compound having a hydroxyl group and a radically polymerizable unsaturated group with an acid anhydride, and reacting a compound having an epoxy group and a radically polymerizable unsaturated group with the resulting carboxyl group, A method of obtaining radically polymerizable resin (I) into which two radically polymerizable unsaturated groups are introduced per molecule of body (B) is mentioned.

  Furthermore, after obtaining the above-mentioned radical polymerizable resin (I), an isocyanate group or a carboxylic acid halide group and a radical are produced in the same manner as in (Method 2) with respect to the hydroxyl group produced by the ring-opening addition reaction of the epoxy group. There is also a method of obtaining a radical polymerizable resin (I) in which three radical polymerizable unsaturated groups are introduced per molecule of the monomer (B) by reacting a compound (D) having a polymerizable unsaturated group. Can be mentioned.

  On the other hand, when the radical polymerizable unsaturated monomer (B) whose functional group (b) is a hydroxyl group is used, the hydroxyl group is reacted with maleic anhydride or itaconic anhydride, and the resulting carboxyl group is converted to an epoxy group. And a compound having a radically polymerizable unsaturated group is reacted to obtain a radically polymerizable resin (I) having two radically polymerizable unsaturated groups introduced per molecule of the monomer (B). It is done.

  Furthermore, after obtaining the above-mentioned radical polymerizable resin (I), an isocyanate group or a carboxylic acid halide group and a radical are produced in the same manner as in (Method 2) with respect to the hydroxyl group produced by the ring-opening addition reaction of the epoxy group. There is also a method of obtaining a radical polymerizable resin (I) in which three radical polymerizable unsaturated groups are introduced per molecule of the monomer (B) by reacting a compound (D) having a polymerizable unsaturated group. Can be mentioned.

  In addition, as the radically polymerizable unsaturated monomer (B), a polymer having two or more reactive functional groups (b) is copolymerized with the compound (A) to obtain a polymer, and then the reaction is performed. A compound having a functional group having reactivity with the functional group (b) and a compound having a radically polymerizable unsaturated group to react with each other, so that two or more radically polymerizable unsaturated groups per molecule of the monomer (B) A method for obtaining a radically polymerizable resin (I) into which is introduced is also mentioned.

  The radical polymerizable resin (I) represented by the radical polymerizable resin (I-1) or the radical polymerizable resin (I-2) has a number average molecular weight (Mn) of the radical polymerizable resin (I). It is preferably in the range of 500 to 5,000, more preferably in the range of 800 to 4,000. The weight average molecular weight (Mw) is preferably in the range of 8,000 to 150,000, and preferably in the range of 10,000 to 100,000. 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 GPC measurement. The measurement conditions for GPC are as follows.
[GPC measurement conditions]
Measuring device: “HLC-8220 GPC” manufactured by Tosoh Corporation
Column: Guard column “HHR-H” manufactured by Tosoh Corporation (6.0 mm ID × 4 cm)
+ "TSK-GEL GMHHR" (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: 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).

  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 30% by mass from the viewpoint of antifouling property of the cured coating film.

  Furthermore, the radical polymerizable unsaturated group content in the radical polymerizable resin (I) is such that the radical polymerizable unsaturated group equivalent is 150 to 500 g / eq. It is preferable from the point which is excellent in the antifouling property of a cured coating film, and it is 200-400 g / eq. It is particularly preferable that the range is

  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 hydroxyl group-containing (meth) acrylate compound. Can be 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 hydroxyl group-containing acrylate compound include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 1,5 -Monohydric alcohols such as pentanediol mono (meth) acrylate, 1,6-hexanediol mono (meth) acrylate, neopentyl glycol mono (meth) acrylate, and hydroxypivalic acid neopentyl glycol mono (meth) acrylate ) Acrylate; trimethylolpropane di (meth) acrylate, ethoxylated trimethylolpropane (meth) acrylate, propoxylated trimethylolpropane di (meth) acrylate, glycerin di (meth) acrylate And di (meth) acrylates of trivalent alcohols such as bis (2- (meth) acryloyloxyethyl) hydroxyethyl isocyanurate, or some of these alcoholic hydroxyl groups were modified with ε-caprolactone Hydroxyl-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 Group-containing compound, or a hydroxyl group-containing polyfunctional (meth) acrylate obtained by modifying the compound with ε-caprolactone; dipropylene glycol mono (meth) acrylate, diethylene glycol mono (meth) acrylate, polypropylene group (Meth) acrylate compounds having an oxyalkylene chain such as coal mono (meth) acrylate and polyethylene glycol mono (meth) acrylate; polyethylene glycol-polypropylene glycol mono (meth) acrylate, polyoxybutylene-polyoxypropylene mono (meth) acrylate (Meth) acrylate compounds having a block structure oxyalkylene chain such as poly (ethylene glycol-tetramethylene glycol) mono (meth) acrylate, poly (propylene glycol-tetramethylene glycol) mono (meth) acrylate, etc. Examples thereof include (meth) acrylate compounds having an oxyalkylene chain.

  The reaction of the above-mentioned aliphatic polyisocyanate compound or aromatic polyisocyanate compound and the hydroxyl 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 hydroxyl group-containing (meth) acrylate compound are excellent in transparency of the cured coating film and have good sensitivity to active energy rays and cure. It is preferable from the point which is excellent in property.

  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% 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 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, a photopolymerization initiator (IV) is added to the active energy ray-curable composition. If necessary, a photosensitizer is further added. 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. There is no.

  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. % 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 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 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 light 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, etc. 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. For example, gravure coater, roll coater, comma coater, knife coater, air knife coater, curtain coater, kiss coater, shower coater, wheeler coater, spin 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 active energy ray-curable coating composition of the present invention is used for a coating material for a protective film for a polarizing plate for a liquid crystal display typified by a TAC film and a color filter for a liquid crystal display (hereinafter referred to as “CF”). Paint, ink or color resist for forming each pixel of RGB; paint for black matrix of CF, ink or black resist; hard coat material for touch panel, mobile phone housing or mobile phone liquid crystal display or organic EL display Hard coating materials, optical fiber cladding materials, optical lenses, waveguides, optical recording media such as DVD and Blu-ray, liquid crystal sealing materials, various optical sealing materials, various protective films, optical adhesives, various optical components, reflection Widely used as an antifouling agent for anti-reflective coatings, antireflection layers, and an antifouling agent for various building materials It is possible to. Among these, it is particularly useful as a coating material for a protective film of a polarizing plate for a liquid crystal display and as a paint / ink or color and black resist for forming or black matrix for each pixel of RGB used in CF.

  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: “Nicolet 380” manufactured by Thermo Electron
The resin solution obtained in each example was measured by the ATR 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 101.6 parts by mass of methyl isobutyl ketone (hereinafter referred to as “MIBK”) as a solvent and stirred at 95 ° C. under a nitrogen stream. The temperature was raised to. Subsequently, 37.9 parts by mass (Liquid 1) of the monomer (A-1-1) obtained in Synthesis Example 1 and 36.1 parts by mass of 2-methacryloyloxyethyl isocyanate (hereinafter referred to as “MOI”). 37.7 parts by mass (Liquid 2) of a solution in which 1.6 parts by mass of MIBK was dissolved, and a solution in which 11.1 parts by mass of azobisdiisobutyronitrile as a radical polymerization initiator was dissolved in 34.3 parts by mass of MIBK. 4 parts by mass (Liquid 3) and 3 types of dropping liquids were set in separate dropping devices, respectively, and dropping was started simultaneously while maintaining the inside of the flask at 95 ° C., and liquid 1 and liquid 2 were 2 hours, and liquid 3 was The solution was added dropwise over 2 hours and 20 minutes. 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 (P1).

  Next, 151.2 parts by mass of methyl ethyl ketone (hereinafter referred to as “MEK”) as a solvent, 0.066 parts by mass of p-methoxyphenol, 0.496 parts by mass of dibutylhydroxytoluene as a polymerization inhibitor, and tin octylate as a urethanization catalyst 0.05 parts by mass were charged, stirring was started under an air stream, and pentaerythritol triacrylate (hereinafter referred to as “PE3A”) and pentaerythritol tetraacrylate (hereinafter referred to as “PE4A”) were maintained at 60 ° C. 97.8 parts by mass (57.7 parts by mass as PE3A) was added dropwise over 1 hour ("Aronix M-305" manufactured by Toagosei Co., Ltd .; PE3A ratio 59 mass%, PE4A ratio 41 mass%). After completion of dropping, the mixture was stirred at 60 ° C. for 2 hours, then heated to 80 ° C. and stirred for 4 hours. Furthermore, 0.113 parts by mass of tin octylate and a mixture of PE3A and PE4A (“Aronix M-305” manufactured by Toagosei Co., Ltd .; PE3A ratio 59 mass%, PE4A ratio 41 mass%) 19.6 parts by mass (as PE3A 11.6 parts by mass), and after stirring at 80 ° C. for 5 hours, the disappearance of the absorption peak of the isocyanate group was confirmed by IR spectrum measurement of the reaction solution.

After cooling the above reaction solution to room temperature, 103.9 parts by mass of MEK was added, and an insoluble material was filtered off by filtration to obtain a MEK solution containing 42.6% by mass of the radical polymerizable resin (I1). As a result of measuring the molecular weight of this radical polymerizable resin (I1) by GPC (polystyrene conversion molecular weight), the number average molecular weight was 1,000, the weight average molecular weight was 98,000, the maximum molecular weight was 3 million, and the fluorine content was 15.3% by weight. , Radical polymerizable unsaturated group equivalent was 207 g / eq. Met. FIG. 1 shows a chart of the IR spectrum of the obtained radical polymerizable resin (I1), and FIG. 2 shows a chart of ¹³ C-NMR.

(Example 2)
A glass flask equipped with a stirrer, a thermometer, a condenser, and a dropping device was charged with 110.0 parts by mass of MIBK as a solvent and heated to 95 ° C. while stirring under a nitrogen stream. Subsequently, 100.7 mass of the solution which melt | dissolved 37.9 mass parts (liquid 1) of monomer (A-1-1) obtained by the said synthesis example 1 and 63.7 mass parts of MOI in 37 mass parts of MIBK. Parts (Liquid 2) and 3 dripping solutions of 56.8 parts by mass (Liquid 3) of 15.2 parts by mass of azobisdiisobutyronitrile as a radical polymerization initiator dissolved in 41.6 parts by mass of MIBK Were set in separate dropping devices, and dropping was started simultaneously while maintaining the inside of the flask at 95 ° C., and liquid 1 and liquid 2 were dropped over 2 hours and liquid 3 was dropped over 2 hours and 20 minutes. 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 (P2).

  Next, 162.2 parts by mass of MEK as a solvent, 0.074 parts by mass of p-methoxyphenol as a polymerization inhibitor, 0.530 parts by mass of dibutylhydroxytoluene, 0.055 parts by mass of tin octylate as a urethanization catalyst were charged, and air Stirring was started under an air stream, and 79.5 parts by mass of 2-hydroxy-3-acryloyloxypropyl methacrylate (hereinafter referred to as “HAPMA”) was added dropwise over 1 hour while maintaining 60 ° C. After completion of dropping, the mixture was stirred at 60 ° C. for 2 hours, then heated to 80 ° C. and stirred for 4 hours. Furthermore, 0.051 part by mass of tin octylate was added, and after stirring at 80 ° C. for 4 hours, disappearance of the absorption peak of the isocyanate group was confirmed by IR spectrum measurement of the reaction solution.

After the reaction solution was cooled to room temperature, 74.4 parts by mass of MEK was added, and a substance insoluble in the solution was separated by filtration to obtain a MEK solution containing 41.1% by mass of the radical polymerizable resin (I2). As a result of measuring the molecular weight of this radical polymerizable resin (I2) by GPC (polystyrene equivalent molecular weight), the number average molecular weight was 3,000, the weight average molecular weight was 33,000, the maximum molecular weight was 1 million, and the fluorine content was 11.4% by weight. , The radical polymerizable unsaturated group equivalent is 230 g / eq. Met. FIG. 3 shows a chart of the IR spectrum of the obtained radical polymerizable resin (I2), and FIG. 4 shows a chart of ¹³ C-NMR.

(Example 3)
A glass flask equipped with a stirrer, a thermometer, a condenser, and a dropping device was charged with 110.7 parts by mass of MIBK as a solvent and heated to 105 ° C. while stirring under a nitrogen stream. Next, a solution 269.3 in which 75.8 parts by mass (Liquid 1) of the monomer (A-1-1) obtained in Synthesis Example 1 and 47.8 parts by mass of MOI were dissolved in 221.5 parts by mass of MIBK. Three types of dropwise addition of 5 parts by mass (liquid 2) and 57.0 parts by mass (liquid 3) of 18.5 parts by mass of azobisdiisobutyronitrile as a radical polymerization initiator dissolved in 28.5 parts by mass of MIBK The liquids were set in separate dropping devices, and dropping was started at the same time while maintaining the inside of the flask at 105 ° C. Liquid 1 and liquid 2 were dropped over 2 hours, and liquid 3 was dropped over 2 hours and 20 minutes. After completion of the dropping, the mixture was stirred at 105 ° C. for 8 hours to obtain a polymer (P3).

  Next, 0.077 parts by mass of p-methoxyphenol, 0.567 parts by mass of dibutylhydroxytoluene as a polymerization inhibitor, and 0.190 parts by mass of tin octylate as a urethanization catalyst were added, and stirring was started under an air stream. While maintaining the temperature, 65.31 parts by mass of HAPMA was added dropwise over 1 hour. After completion of dropping, the mixture was stirred at 60 ° C. for 2 hours, then heated to 80 ° C. and stirred for 17 hours. Furthermore, 0.095 parts by mass of tin octylate was added and stirred at 80 ° C. for 4 hours, and then the disappearance of the absorption peak of the isocyanate group was confirmed by IR spectrum measurement of the reaction solution.

After cooling the above reaction solution to room temperature, 63.4 parts by mass of MEK was added, and a substance insoluble in the solution was filtered off to obtain a MIBK solution containing 30.2% by mass of the radical polymerizable resin (I3). . As a result of measuring the molecular weight of the radical polymerizable resin (I3) by GPC (polystyrene equivalent molecular weight), the number average molecular weight was 2,200, the weight average molecular weight was 35,000, the maximum molecular weight was 1 million, and the fluorine content was 22.9% by weight. , Radical polymerizable unsaturated group equivalent was 308 g / eq. Met. FIG. 5 shows a chart of the IR spectrum of the obtained radical polymerizable resin (I3), and FIG. 6 shows a chart of ¹³ C-NMR.

Example 4
A glass flask equipped with a stirrer, a thermometer, a condenser, and a dropping device was charged with 128.6 parts by mass of MIBK as a solvent and heated to 105 ° C. while stirring under a nitrogen stream. Next, a solution obtained by dissolving 37.9 parts (liquid 1) of the monomer (A-1-1) obtained in Synthesis Example 1 above and 80.9 parts by mass of MOI in 52.2 parts by mass of MIBK 133. 3 parts of 1 part by weight (Liquid 2) and 57.6 parts by weight (Liquid 3) of 17.8 parts by weight of azobisdiisobutyronitrile as a radical polymerization initiator dissolved in 39.8 parts by weight of MIBK The dropping liquids were set in separate dropping apparatuses, respectively, and dropping was started simultaneously while maintaining the inside of the flask at 105 ° C., and liquid 1 and liquid 2 were dropped over 2 hours and liquid 3 was dropped over 2 hours and 20 minutes. After completion of dropping, the mixture was stirred at 105 ° C. for 10 hours to obtain a polymer (P4).

  In a glass flask equipped with a stirrer, thermometer, condenser, and dropping device, 50 parts by mass of the polymer (P4) obtained by the above synthesis, 0.04 parts by mass of p-methoxyphenol as a polymerization inhibitor, dibutylhydroxy 0.30 part by mass of toluene and 0.04 part by mass of tin octylate as a urethanization catalyst were added, stirring was started under an air stream, and bis (2-acryloyloxyethyl) hydroxyethyl isocyanurate (hereinafter referred to as 60 ° C.) , "BAEHI") and tris (2-acryloyloxyethyl) isocyanurate (hereinafter referred to as "TAEI") ("Aronix M-313" manufactured by Toagosei Co., Ltd.); BAEHI ratio 35 mass%, TAEI 87.9 parts by mass (a ratio of 65% by mass) (28.8 parts by mass as BAEHI) was added dropwise over 1 hour. After completion of the dropwise addition, the mixture was stirred at 60 ° C. for 2 hours, then heated to 80 ° C. and stirred for 7 hours to carry out the reaction. Further, a mixture of BAEHI and TAEI (“Aronix M-313” manufactured by Toagosei Co., Ltd .; BAEHI ratio 35% by mass, TAEI ratio 65% by mass) 1.65 parts by mass (0.58 parts by mass as BAEHI), octylic acid After adding 0.12 parts by mass of tin and stirring at 80 ° C. for 15 hours, the disappearance of the absorption peak of the isocyanate group was confirmed by IR spectrum measurement of the reaction solution.

After cooling the above reaction solution to room temperature, 103.1 parts by mass of MEK was added, and an insoluble matter was separated by filtration to obtain a MIBK solution containing 38.6% by mass of the radical polymerizable resin (I4). The molecular weight of the radical polymerizable resin (I4) was measured by GPC (polystyrene equivalent molecular weight). As a result, the number average molecular weight was 1,800, the weight average molecular weight was 18,000, the maximum molecular weight was 500,000, and the fluorine content was 6.8% by weight. , Radical polymerizable unsaturated group equivalent was 291 g / eq. Met. FIG. 7 shows a chart of an IR spectrum of the obtained radical polymerizable resin (I4), and FIG. 8 shows a chart of ¹³ C-NMR.

(Example 5)
A glass flask equipped with a stirrer, a thermometer, a condenser, and a dropping device was charged with 88 parts by mass of MIBK as a solvent and heated to 105 ° C. while stirring under a nitrogen stream. Next, 84 parts by mass (Liquid 1) of monomer (A-1-1) obtained in Synthesis Example 1 and 51 parts by mass of glycidyl methacrylate (hereinafter referred to as “GMA”) were added to 126.8 parts by mass of MIBK. 170.9 parts by mass (solution 2) of a solution dissolved in 20.8 parts by mass of MIBK and 20.8 parts by mass of t-butyl-2-ethylhexanoate as a radical polymerization initiator in 100.6 parts by mass of MIBK Three types of dropping liquids with parts by mass (Liquid 3) were set in separate dropping devices, and dropping was started simultaneously while maintaining the inside of the flask at 105 ° C. Liquid 1 and liquid 2 were 2 hours, and liquid 3 was 2 It was added dropwise over a period of 20 minutes. After completion of dropping, the mixture was stirred at 105 ° C. for 7 hours, and then the solvent was distilled off to obtain a polymer (P4).

  Next, 21.5 parts by mass of methyl isobutyl ketone as a solvent, 0.084 parts by mass of p-methoxyphenol, 0.630 parts by mass of dibutylhydroxytoluene, and acrylic acid (hereinafter referred to as “AA”) 24.8 as a polymerization inhibitor. A mass part and 0.809 part by mass of triphenylphosphine were charged, stirring was started under a nitrogen stream, and the reaction was carried out by stirring at 120 ° C. for 7 hours. Next, 104.2 parts by mass of MIBK as a solvent and 0.053 parts by mass of tin octylate as a urethanization catalyst were charged, stirring was started under an air stream, and 2-acryloyloxyethyl isocyanate (hereinafter, “ "AOI") 48.5 parts by mass was added dropwise over 1 hour. 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 the above reaction liquid to room temperature, 104.2 parts by weight of MIBK was added, and a substance insoluble in the solution was filtered off to obtain a MIBK solution containing 40.4% by weight of the radical polymerizable resin (I5). . The molecular weight of the radical polymerizable resin (I5) was measured by GPC (polystyrene equivalent molecular weight). As a result, the number average molecular weight was 2,100, the weight average molecular weight was 14,000, the maximum molecular weight was 1 million, and the fluorine content was 22.9% by weight. , The radical polymerizable unsaturated group equivalent was 303 g / eq. Met. FIG. 9 shows a chart of the IR spectrum of the obtained radical polymerizable resin (I5), and FIG. 10 shows a chart of ¹³ C-NMR.

(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 MIBK as a solvent and heated to 105 ° C. while stirring under a nitrogen stream. Next, 40 parts by mass of an acrylate having a fluorinated alkyl group represented by the following formula (Y-1) (hereinafter referred to as “PFA”) and 2-hydroxyethyl methacrylate (hereinafter referred to as “HEMA”) 28.8 137.8 parts by mass of a monomer solution obtained by mixing part by mass and 69 parts by mass of MIBK as a solvent, 3.4 parts by mass of t-butylperoxy-2-ethylhexanoate as a radical polymerization initiator, and MIBK 22.5 as a solvent Two types of dropping solutions of 25.9 parts by mass of the initiator solution mixed with parts by mass were set in separate dropping devices, respectively, and dropped simultaneously over 3 hours while maintaining the inside of the flask at 105 ° C. After completion of the dropping, the mixture was stirred at 105 ° C. for 10 hours to obtain a fluorinated curable resin.

  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 added, and 31.2 parts by mass of AOI was added dropwise over 1 hour while maintaining 60 ° C. in an air stream. did. 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 MIBK 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.

  Table 1 shows the raw materials and characteristic values of the radical polymerizable resins (I1) to (I5) obtained in Examples 1 to 5.

(Preparation of base resin composition of active energy ray-curable coating composition)
As an ultraviolet 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, and 1-hydroxycyclohexyl phenyl ketone (Ciba Specialty Chemicals) as a photopolymerization initiator "Irgacure 184" manufactured by the company) 5 parts by mass, 54 parts by mass of toluene as a solvent, 28 parts by mass of 2-propanol, 28 parts by mass of ethyl acetate, 28 parts by mass of propylene glycol monomethyl ether A base resin composition of the coating composition was obtained.

(Examples 6 to 10, Comparative Examples 2 to 3)
To the 268 parts by mass of the base resin composition obtained above, the radical polymerizable resin solutions obtained in Examples 1 to 5 and Comparative Example 1 were added in an amount of 1 part by mass and mixed uniformly. An active energy ray-curable coating composition was obtained. Next, this active energy ray-curable coating composition was applied to a bar coater No. 13 was applied to a TAC film having a thickness of 80 μm, and then put into a dryer at 60 ° C. for 5 minutes to volatilize the solvent, and an ultraviolet curing device (in a nitrogen atmosphere, using a high pressure mercury lamp, an ultraviolet irradiation amount of ² kJ / m ^2). ) To produce coated films as Examples 5 to 8 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 2.

  The cured coating film of the active energy ray-curable coating composition of Examples 6 to 10 to which the radical polymerizable resin obtained in Examples 1 to 5 which is the fluorine-containing curable resin of the present invention was added was made of strong alkaline water. Even if it processed, the stain | pollution | contamination prevention property and dirt wiping off property did not fall. On the other hand, in Comparative Example 3 using the radical polymerizable resin (Z-1), a decrease was observed in the stain adhesion preventing property and the stain wiping property after treatment with strong alkaline water. In Comparative Example 4 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 (9)

  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 ) As an essential monomer component, and the monomer (B) using the reactive functional group (b) of the monomer (B). ) A fluorine-containing curable resin, which is a radically polymerizable resin (I) into which two or more radically polymerizable unsaturated groups are introduced per molecule.   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 ) As an essential monomer component, a functional group (c) having reactivity with the functional group (b) and two or more radical polymerizable unsaturated groups. The fluorine-containing curable resin according to claim 1, which is a radical polymerizable resin (I) obtained by reacting a compound (C) having:   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. Fluorine-containing curable resin.   Radical polymerizability having a poly (perfluoroalkylene ether) chain and a compound (A) having a structural moiety having a radically polymerizable unsaturated group at both ends and a cyclic ether group (b ′) capable of undergoing a ring-opening addition reaction A functional group (P ′) obtained by copolymerizing an unsaturated monomer (B ′) as an essential monomer component with addition reactivity to the cyclic ether group (b ′) ( c ′) and a compound (C ′) having a radically polymerizable unsaturated group are reacted, and then an isocyanate group or a carboxylic acid halide group and a radically polymerizable unsaturated group are added to the hydroxyl group produced by the reaction. The fluorine-containing curable resin according to claim 1, which is a radically polymerizable resin (I) obtained by reacting the compound (D) having the compound.   5. The poly (perfluoroalkylene ether) chain contained in the resin structure of the radical polymerizable resin (I) contains 25 to 80 fluorine atoms per chain. The fluorine-containing curable resin as described.   A cured product obtained by applying the fluorine-containing curable resin according to any one of claims 1 to 5 to a base material and irradiating with an active energy ray to be cured.   An activity comprising the fluorine-containing curable resin according to any one of claims 1 to 5, 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 6 which uses the fluorine-containing curable resin of any one of Claims 1-5 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 7 or 8 to a substrate and irradiating and curing the active energy ray.

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