JP5581943B2 - Fluorine-containing polymerizable resin, active energy ray-curable coating composition and cured product thereof - Google Patents

Description

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

  In recent years, liquid crystal displays, plasma displays, organic EL displays, etc., which are flat panel displays (FPDs), such as home televisions, notebook computers, tablet computers, electronic book terminals, mobile phones, car navigation systems for automobiles, It is applied to operation panels of various devices. However, these FPDs have a problem that it is difficult to see the display because dirt such as fingerprints adheres to the display surface. In particular, touch panels using a display screen of a mobile phone, which is frequently touched by the skin, a car navigation system for automobiles, or an operation panel of various devices as an operation panel, prevent adhesion of dirt such as fingerprints, that is, antifouling property. Is required.

  In addition, in electronic terminals such as tablet computers, the display screen is a touch panel, and it is common to operate by sliding a finger on the display screen. Sliding properties are also necessary.

  As a method for imparting antifouling properties and slipperiness as described above, a method of forming a coating film by coating the outermost surface of a screen with a coating composition containing a fluorosurfactant has been proposed. However, simply adding a fluorosurfactant to the coating composition causes a problem that the fluorosurfactant falls off the coating film over time, and the initial antifouling property and slipperiness cannot be maintained.

  Therefore, in order to prevent such deterioration of antifouling property and slipperiness over time, monoacrylate having a fluorinated alkyl group is copolymerized with an acrylic monomer having active hydrogen, and then obtained. A polymerizable fluorosurfactant having an unsaturated group obtained by reacting an acrylic monomer having an isocyanate group with a polymer has been proposed (for example, see Patent Document 1). However, this polymerization type fluorosurfactant can prevent deterioration of antifouling property and slipperiness over time, but has a problem that initial antifouling property and slipperiness are not sufficient.

  In addition, as in the case of the above-described polymerization type fluorine-containing surfactant, a polysiloxane produced using a compound having a relatively low molecular weight (perfluoroalkylene ether) chain and having di (meth) acryloyl groups at both ends thereof. A polymerization type fluorine-containing surfactant having a (perfluoroalkylene ether) chain and an unsaturated group has been proposed (for example, see Patent Document 2). The fluorine-containing surfactant having a poly (perfluoroalkylene ether) chain is improved in antifouling property and slipperiness than that described in Patent Document 1, but requires a higher level of antifouling property and slipperiness. I was not satisfied.

JP 2007-246696 A International Publication WO2009 / 133770

  The problem to be solved by the present invention is that the surface of the coating film can be provided with excellent antifouling property and slipperiness, and can be used as a fluorine-based surfactant or a fluorine-based surface modifier. It is to provide a resin. In addition, it is possible to prevent volatilization and detachment of the fluorosurfactant or its decomposition products from the coating surface after being applied and cured, and to improve the stability of antifouling and slippery surface performance. It is to provide an active energy ray-curable coating composition and a cured product thereof.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that a poly (perfluoroalkylene ether) chain having a specific molecular weight and a compound having radically polymerizable unsaturated groups at both ends thereof, a polymerizable property, A fluorine-containing polymerizable resin in which a polymerizable unsaturated group is introduced into the reactive group after copolymerization with a radically polymerizable unsaturated monomer having a reactive group capable of introducing an unsaturated group It has been found that by using it as a surfactant or a fluorine-based surface modifier, an excellent antifouling property can be imparted to the surface of the coating film, and the present invention has been completed.

That is, the present invention includes a poly-average molecular weight of 3, 0 00-4 5 00 has a (perfluoroalkylene ether) chain, a compound having a radically polymerizable unsaturated group at both ends (A), The polymer (P) obtained by copolymerizing a radically polymerizable unsaturated monomer (B) having a reactive group (b) as an essential monomer component in a fluorine-based solvent is added to the reactive group. (B) a fluorine-containing polymerizable resin obtained by reacting a compound (C) having a reactive functional group (c) and a radically polymerizable unsaturated group,
The monomer (B) has a radically polymerizable unsaturated monomer having at least one reactive group selected from the group consisting of a hydroxyl group, an isocyanate group, an epoxy group and a carboxyl group, or a radically polymerizable unsaturated group A carboxylic acid halide or a carboxylic acid anhydride,
The compound (C) is a compound having at least one functional group selected from the group consisting of a hydroxyl group, an isocyanate group, an epoxy group and a carboxyl group and a radical polymerizable unsaturated group, or a carboxylic acid having a radical polymerizable unsaturated group The present invention relates to a fluorine-containing polymerizable resin, which is a halide or a carboxylic acid anhydride, and a cured product of the resin.

  Moreover, this invention relates to the hardened | cured material formed by apply | coating this composition to a base material, irradiating an active energy ray, and hardening | curing this composition which mix | blended the said fluorine-containing polymeric resin.

  The fluorine-containing polymerizable resin of the present invention can impart antifouling property and slipperiness to the substrate surface by being applied to the substrate alone to form a cured coating film. In addition, the active energy ray-curable composition containing the fluorine-containing polymerizable resin as a fluorine-containing surfactant has the effect of minimizing the surface free energy peculiar to fluorine atoms when applied to a substrate. Thus, the fluorine-containing polymerizable resin is segregated on the surface of the coating film, and surface modification that imparts antifouling properties and slipperiness only to the coating film surface is possible. Furthermore, since the fluorine-containing polymerizable resin can be polymerized with other polymerizable components in the active energy ray-curable composition, the fluorine-containing polymerizable resin of the present invention is stronger in the cured coating film. Therefore, volatilization and desorption of the fluorine-containing polymerizable resin or a decomposition product thereof can be suppressed from the surface of the cured coating film even if heat treatment, washing, or the like is performed. Furthermore, the cured coating film using the fluorine-containing polymerizable resin of the present invention maintains excellent antifouling properties even when the surface of the cured coating film is repeatedly wiped off and the coating film surface is worn. can do.

  Accordingly, the cured coating film using the fluorine-containing polymerizable resin of the present invention has excellent antifouling property, slipperiness and antifouling durability on the surface, and thus is a liquid crystal which is a flat panel display (FPD). Display, plasma display, organic EL display, etc. shall be formed on the outermost surface of the display device such as home TV, notebook computer, tablet computer, electronic book terminal, mobile phone, car navigation for automobiles, operation panel of various devices. Therefore, when touching the display screen directly with your finger, it has excellent antifouling properties and good dirt wiping properties to prevent fingerprints and other dirt, and good operability when sliding your finger on the display screen. The slipperiness which exhibits can be provided.

FIG. 1 is an IR spectrum chart of the fluorine-containing polymerizable resin (1) obtained in Example 1. FIG. 2 is a GPC chart of the fluorine-containing polymerizable resin (1) obtained in Example 1. FIG. 3 is an IR spectrum chart of the fluorine-containing polymerizable resin (2) obtained in Example 2. FIG. 4 is a GPC chart of the fluorine-containing polymerizable resin (2) obtained in Example 2.

  The fluorine-containing polymerizable resin of the present invention comprises a compound (A) having a poly (perfluoroalkylene ether) chain having an average molecular weight of 2,500 to 10,000 and having a polymerizable unsaturated group at both ends thereof. The polymer (P) obtained by copolymerizing a polymerizable unsaturated monomer (B) having a reactive group (b) as an essential monomer component is reactive with the functional group (b). It is a polymerizable resin having a polymerizable unsaturated group obtained by reacting a compound (C) having a functional group (c) having a polymerizable unsaturated group.

  In addition, examples of the poly (perfluoroalkylene ether) chain include those having a structure in which a divalent fluorocarbon group having 1 to 3 carbon atoms and oxygen atoms are alternately connected. The divalent fluorocarbon group having 1 to 3 carbon atoms may be one kind or a mixture of a plurality of kinds, and specifically, those represented by the following structural formula (a1) Can be mentioned.

（上記構造式（ａ）中、Ｘは下記構造式（ａ１−１）〜（ａ１−５）であり、構造式（ａ１）中の全てのＸが同一構造のものであってもよいし、また、複数の構造がランダムに又はブロック状に存在していてもよい。また、ｎは繰り返し単位数を表す整数である。）

(In the structural formula (a), X is the following structural formulas (a1-1) to (a1-5), and all X in the structural formula (a1) may have the same structure, In addition, a plurality of structures may be present randomly or in blocks, and n is an integer representing the number of repeating units.

  Among these, the perfluoromethylene structure represented by the structural formula (a1-1) and the structure in that the coating film surface has particularly good wiping properties and excellent antifouling properties. Those coexisting with the perfluoroethylene structure represented by the formula (a1-2) are particularly preferable. Here, the abundance ratio between the perfluoromethylene structure represented by the structural formula (a1-1) and the perfluoroethylene structure represented by the structural formula (a1-2) is a molar ratio [structure (a1- 1) / structure (a1-2)] is preferably 1/10 to 10/1 in terms of antifouling property, and the value of n in the structural formula (a1) is 30 to 80 The range of 35 to 60 is particularly preferable.

  As a compound before introduce | transducing a polymerizable unsaturated group into the both terminal used as the raw material of the said compound (A), the following general formula (a2-1)-(a2-6) etc. are mentioned, for example. In the following structural formulas, “—PFPE—” represents the poly (perfluoroalkylene ether) chain.

  The compound (A) used in the present invention includes a poly (perfluoroalkylene ether) chain portion represented by “—PFPE—” in the above general formula (up to carbon atoms having fluorine atoms at both ends in the chain) The average molecular weight of the poly (perfluoroalkylene ether) chain in the range of 2,500 to 10,000 is higher than the antifouling property and slipperiness, and the active energy ray-curable composition. In order to make the compatibility with the base resin good, those in the range of 2,800 to 5,000 are preferable, and those in the range of 3,000 to 4,500 are more preferable.

In addition, as a measuring method of the average molecular weight of the said poly (perfluoroalkylene ether) chain | strand part, in the case of the compound represented, for example by the following general formula (a2-1-1), ¹⁹ F-NMR is measured and a hydroxyl group is measured. And the integral ratio of the chemical shift of the CF ₂ part adjacent via methylene, the chemical shift of the perfluoromethylene group (—CF ₂ —), the chemical shift of the perfluoroethylene group (—CF ₂ CF ₂ —), etc. After obtaining, the integration ratio of the chemical shift of the CF ₂ portion adjacent to each other through the hydroxyl group and methylene is set to 4, so that the number of other perfluoromethylene groups, perfluoroethylene groups, etc. can be calculated from the respective integration ratios. Can be sought.

（式中、ｐ及びｑはそれぞれ独立に１以上の整数を表す。）

(In the formula, p and q each independently represents an integer of 1 or more.)

  Examples of the radically polymerizable unsaturated group at both ends of the chain of the compound (A) include those having radically polymerizable unsaturated groups represented by the following structural formulas U-1 to U-5.

  Among these radically polymerizable unsaturated groups, in particular, the structural formula is obtained from the point that the compound (A) itself is easily available and manufactured, or has excellent reactivity with the radically polymerizable unsaturated monomer (B) described later. An acryloyloxy group represented by U-1 and a methacryloyloxy group represented by Structural Formula U-2 are preferred. Moreover, since chemical resistance improves, the methacryloyloxy group represented by Structural formula U-2 and the styryl methoxy group represented by Structural formula U-5 are preferable.

  Among the compounds (A), those having the acryloyloxy group or methacryloyloxy group include those represented by the following structural formulas (A-1) to (A-13). In the following structural formulas, “—PFPE—” represents a poly (perfluoroalkylene ether) chain.

  Among these, the structural formulas (A-1), (A) are particularly easy because the industrial production of the compound (A) itself is easy, and the polymerization reaction when producing the polymer (P) is also easy. -2), (A-5), and those represented by (A-6) are preferred. Moreover, since chemical resistance improves, the said structural formula (A-2), (A-4), (A-12), (A-13) is preferable.

  In order to produce the compound (A), for example, a 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) acryloyl group” refers to one or both of methacryloyl group and acryloyl group. “Acrylic acid” refers to one or both of methacrylic acid and acrylic acid.

  The polymerizable unsaturated monomer (B) is a radical polymerizable unsaturated monomer having at least one reactive group selected from the group consisting of a hydroxyl group, an isocyanate group, an epoxy group and a carboxyl group, or a radical polymerizable property. A carboxylic acid halide or carboxylic acid anhydride having an unsaturated group. The polymerizable unsaturated monomer (B) preferably has a radically polymerizable unsaturated group and a radically polymerizable carbon-carbon unsaturated double bond, more specifically, a vinyl group, (meth) acryloyl. Group, maleimide group, and the like, and a (meth) acryloyl group is more preferable from the viewpoint of easy polymerization.

  Specific examples of the polymerizable unsaturated monomer (B) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) ) Acrylate, 4-hydroxybutyl (meth) acrylate, 1,4-cyclohexanedimethanol mono (meth) acrylate, N- (2-hydroxyethyl) (meth) acrylamide, glycerin mono (meth) acrylate, polyethylene glycol mono (meta) ) Acrylate, polypropylene glycol mono (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2- (meth) acryloyloxyethyl-2-hydroxyethyl phthalate, terminal hydroxyl group-containing lactone modified (meth) ) Hydroxyl-containing unsaturated monomers such as acrylate; 2- (meth) acryloyloxyethyl isocyanate, 2- (2- (meth) acryloyloxyethoxy) ethyl isocyanate, 1,1-bis ((meth) acryloyloxymethyl) Isocyanate group-containing unsaturated monomers such as ethyl isocyanate; Epoxy group-containing unsaturated monomers such as glycidyl methacrylate and 4-hydroxybutyl acrylate glycidyl ether; (meth) acrylic acid, 2- (meth) acryloyloxyethyl succinic acid Carboxyl group-containing unsaturated monomers such as 2- (meth) acryloyloxyethylphthalic acid, maleic acid and itaconic acid; radical polymerizable unsaturated groups such as (meth) acrylic acid chloride and (meth) acrylic acid bromide. Carboxylic acid halide having: None Maleic acid, and the like acid anhydride having an unsaturated double bond such as itaconic anhydride.

  When manufacturing the said polymer (P), you may use the other polymerizable unsaturated monomer copolymerizable with these other than the said compound (A) and a monomer (B). 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) (Meth) acrylates such as 2-ethylhexyl acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate Polyethers such as polypropylene glycol mono (meth) acrylate and polyethylene glycol mono (meth) acrylate (Meth) acrylate having a chain; aromatic vinyls such as styrene, α-methylstyrene, p-methylstyrene, p-methoxystyrene; maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide And maleimides such as dodecylmaleimide, stearylmaleimide, phenylmaleimide, cyclohexylmaleimide and the like.

  The method for producing the polymer (P) is a radical polymerization initiator in the organic solvent with the compound (A) and the monomer (B) and, if necessary, other polymerizable unsaturated monomers. And a method of copolymerization in the presence of. Examples of the organic solvent used here include fluorine-based solvents, ketone-based solvents, ester-based solvents, amide-based solvents, sulfoxide-based solvents, ether-based solvents, and hydrocarbon-based solvents. Specific examples of these organic solvents include, for example, metaxylene hexafluoride, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, dimethylformamide, dimethylacetamide, and N-methylpyrrolidone. , Dimethyl sulfoxide, diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, toluene, xylene and the like. These organic solvents can be selected as appropriate in consideration of the boiling point, compatibility with the raw material or polymer, and polymerizability. Among these organic solvents, the raw materials such as the compound (A) and the monomer (B) and the polymer (P) to be produced have good solubility, and the boiling point is relatively high. Metaxylene hexafluoride is more preferred because it can also promote the progress of. These organic solvents can be used alone or in combination of two or more.

  Examples of the radical polymerization initiator include acetyl peroxide, cumyl peroxide, t-butyl peroxide, propionyl peroxide, benzoyl peroxide, 2-chlorobenzoyl peroxide, 3-chlorobenzoyl peroxide, 4-hydroxy peroxide. Chlorobenzoyl, 2,4-dichlorobenzoyl peroxide, 4-bromomethylbenzoyl peroxide, lauroyl peroxide, diisopropyl peroxycarbonate, tetralin hydroperoxide, 1-phenyl-2-methylpropyl-1-hydroperoxide, pertriphenylacetic acid t-butyl, t-butyl hydroperoxide, t-butyl performate, t-butyl peracetate, t-butyl perbenzoate, t-butyl perethylhexanoate, t-butyl perphenylacetate, per-4-methoxy Peroxides such as t-butyl acetate; 2,2′-dichloro-2,2′-azo Bispropane, 1,1′-azo (methylethyl) diacetate, 2,2′-azobis (2-amidinopropane) nitrate, 2,2′-azobisisobutane, 2,2′-azobisisobutyramide, 2 2,2′-azobisisobutyronitrile, methyl 2,2′-azobis-2-methylpropionate, 2,2′-dichloro-2,2′-azobisbutane, 2,2′-azobis-2-methylbutyrate Ronitrile, dimethyl 2,2′-azobisisobutyrate, dimethyl 2,2′-azobisisobutyrate, 2- (4-methylphenylazo) -2-methylmalonodinitrile, 4,4′-azobis-4-cyanovaleric acid 3,5-dihydroxymethylphenylazo-2-methylmalonodinitrile, 1,1′-azobis-1-cyclohexanecarbonitrile, 1,1′-azobis- -Phenylethane, 1,1'-azobiscumene, ethyl 4-nitrophenylazobenzylcyanoacetate, phenylazodiphenylmethane, phenylazotriphenylmethane, 4-nitrotriphenylazotriphenylmethane, 1,1'-azobis-1 And azo compounds such as 2-diphenylethane. Furthermore, a chain transfer agent such as lauryl mercaptan, 2-mercaptoethanol, thioglycerol, ethylthioglycolic acid, octylthioglycolic acid or the like can be used as necessary.

  A functional group (c) having reactivity with the reactive group (b) of the monomer (B) used as a raw material for the polymer (P) is added to the polymer (P) obtained as described above. ) And the compound (C) having a radically polymerizable unsaturated group are reacted to obtain the fluorine-containing polymerizable resin of the present invention.

  The compound (C) is a compound having at least one functional group selected from the group consisting of a hydroxyl group, an isocyanate group, an epoxy group and a carboxyl group and a radically polymerizable unsaturated group, or a carboxylic acid having a radically polymerizable unsaturated group Halide or carboxylic anhydride.

  As a combination of the monomer (B) and the compound (C), when the monomer (B) is a monomer having a hydroxyl group, the compound (C) has an isocyanate group, a carboxyl group, an epoxy group, and a radical polymerizable property. In the case of a compound having an unsaturated group, or a carboxylic acid halide or carboxylic acid anhydride having a radically polymerizable unsaturated group, and the monomer (B) is a monomer having an isocyanate group, the compound (C) is A compound having a hydroxyl group and a radically polymerizable unsaturated group, and when the monomer (B) is a monomer having an epoxy group, the compound (C) is a compound having a hydroxyl group, a carboxyl group and a radically polymerizable unsaturated group Or when the monomer (B) is a monomer having a carboxyl group, the compound (C) is a hydroxyl group or an epoxy group. A compound having a fine radically polymerizable unsaturated group. These may be combined with a plurality of types.

  Specific examples of the compound (C) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxy Butyl (meth) acrylate, 1,4-cyclohexanedimethanol mono (meth) acrylate, N- (2-hydroxyethyl) (meth) acrylamide, glycerin mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (Meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2- (meth) acryloyloxyethyl-2-hydroxyethyl phthalate, terminal hydroxyl group-containing lactone-modified (meth) acrylate Hydroxyl group-containing unsaturated monomers such as 2- (meth) acryloyloxyethyl isocyanate, 2- (2- (meth) acryloyloxyethoxy) ethyl isocyanate, 1,1-bis ((meth) acryloyloxymethyl) ethyl Isocyanate group-containing unsaturated monomers such as isocyanate; Epoxy group-containing unsaturated monomers such as glycidyl methacrylate and 4-hydroxybutyl acrylate glycidyl ether; (meth) acrylic acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (Meth) acryloyloxyethylphthalic acid, maleic acid, itaconic acid and other carboxyl group-containing unsaturated monomers; (meth) acrylic acid chloride, (meth) acrylic acid bromide and other radical polymerizable unsaturated groups Carboxylic acid halide; maleic anhydride An acid anhydride having an unsaturated double bond such as itaconic acid. Moreover, 2-hydroxy-3-acryloyloxypropyl methacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate etc. can also be used as what has a some radical polymerizable unsaturated group.

  Among these compounds (C), since the fluorinated polymerizable resin of the present invention is used alone or as an additive to the active energy ray-curable composition, it has high curability, so that 2-hydroxyethyl acrylate, 2 -Hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, 4-hydroxybutyl acrylate, 1,4-cyclohexanedimethanol monoacrylate, N- (2-hydroxyethyl) acrylamide, 2-acryloyloxyethyl isocyanate, 4-hydroxybutyl acrylate glycidyl ether and acrylic acid are preferred.

  The method of reacting the polymer (P) with a compound (C) containing a functional group (c) having reactivity with the reactive group (b) and a radically polymerizable unsaturated group is a compound (C ) In which the radically polymerizable unsaturated group 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 monomer (B) is a monomer having a hydroxyl group and the compound (C) is a compound having an isocyanate group and a radically polymerizable unsaturated group, or the monomer (B ) Is a monomer having an isocyanate group, and the compound (C) is a compound having a hydroxyl group and a radical polymerizable unsaturated group, p-methoxyphenol, hydroquinone, 2,6-di- -T-butyl-4-methylphenol or the like is used, dibutyltin dilaurate, dibutyltin diacetate, tin octylate, zinc octylate or the like is used as the urethanization reaction catalyst, and the reaction temperature is in the range of 20 to 150 ° C. In particular, a method of reacting in the range of 40 to 120 ° C. is preferable. When the monomer (B) is a monomer having an epoxy group and the compound (C) is a compound having a carboxyl group and a radically polymerizable unsaturated group, or the monomer ( When B) is a monomer having a carboxyl group and the compound (C) is a compound having an epoxy group and a radically polymerizable unsaturated group, p-methoxyphenol, hydroquinone, 2,6 as a polymerization inhibitor -Tertiary amines such as triethylamine, quaternary ammoniums such as tetramethylammonium chloride, and tertiary amines such as triphenylphosphine as esterification reaction catalysts using di-t-butyl-4-methylphenol Use phosphines, quaternary phosphoniums such as tetrabutylphosphonium chloride, etc. and react at a reaction temperature of 80 to 130 ° C., particularly 100 to 120 ° C. So it is preferable to be.

  Examples of the organic solvent used in the above reaction include a fluorine solvent, a ketone solvent, an ester solvent, an amide solvent, a sulfoxide solvent, an ether solvent, and a hydrocarbon solvent. Specific examples of these organic solvents include, for example, metaxylene hexafluoride, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, dimethylformamide, dimethylacetamide, and N-methylpyrrolidone. , Dimethyl sulfoxide, diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, toluene, xylene and the like. These organic solvents can be selected as appropriate in consideration of the boiling point, compatibility with the raw material or polymer, and polymerizability. Among these organic solvents, metaxylene hexafluoride is more preferable because the solubility of the polymer (P) and the compound (C) is good. These organic solvents can be used alone or in combination of two or more.

  The fluorine-containing polymerizable resin of the present invention obtained as described above can prevent gelation during production and can impart excellent antifouling properties to the cured coating film, so that its number average molecular weight (Mn) is 1, The range is preferably from 000 to 20,000, and more preferably from 1,500 to 10,000. Moreover, it is preferable that a weight average molecular weight (Mw) is the range of 1,000-20,000, and it is preferable that it is the range of 2,000-10,000. In addition, a number average molecular weight (Mn) and a weight average molecular weight (Mw) are the values converted into polystyrene based on said GPC measurement. In addition, the number average molecular weight (Mn) and the weight average molecular weight (Mw) here were measured in the above-described polymerization operation in a state including by-products such as a homopolymer of the monomer (B) generated. Is.

  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-N" (7.8 mm ID x 30 cm) manufactured by Tosoh Corporation
+ "TSK-GEL GMHHR-N" (7.8 mm ID x 30 cm) manufactured by Tosoh Corporation
+ "TSK-GEL GMHHR-N" (7.8 mm ID x 30 cm) manufactured by Tosoh Corporation
+ "TSK-GEL GMHHR-N" (7.8 mm ID x 30 cm) manufactured by Tosoh Corporation
Detector: ELSD ("ELSD2000" manufactured by Oltec)
Data processing: “GPC-8020 Model II data analysis version 4.30” manufactured by Tosoh Corporation
Measurement conditions: Column temperature 40 ° C
Developing solvent Tetrahydrofuran (THF)
Flow rate 1.0 ml / min Sample: A 1.0% by mass tetrahydrofuran solution filtered in terms of resin solids through a microfilter (100 μl).
Standard sample: The following monodisperse polystyrene having a known molecular weight was used in accordance with the measurement manual of “GPC-8020 Model II Data Analysis Version 4.30”.

(Monodispersed polystyrene)
“A-500” manufactured by Tosoh Corporation
"A-1000" manufactured by Tosoh Corporation
"A-2500" manufactured by Tosoh Corporation
"A-5000" manufactured by Tosoh Corporation
“F-1” manufactured by Tosoh Corporation
"F-2" manufactured by Tosoh Corporation
“F-4” manufactured by Tosoh Corporation
“F-10” manufactured by Tosoh Corporation
“F-20” manufactured by Tosoh Corporation
“F-40” manufactured by Tosoh Corporation
“F-80” manufactured by Tosoh Corporation
“F-128” manufactured by Tosoh Corporation
“F-288” manufactured by Tosoh Corporation
“F-550” manufactured by Tosoh Corporation

  In addition, the fluorine content in the fluorine-containing polymerizable resin of the present invention is preferably in the range of 2 to 50% by mass because both antifouling properties and compatibility with other components can be achieved. The range of 40% by mass is more preferable, and the range of 10 to 35% by mass is more preferable. The fluorine content in the fluorine-containing radical polymerizable copolymer of the present invention is a value calculated from the mass ratio of fluorine atoms with respect to the total amount of raw materials used.

  Furthermore, the content of the radically polymerizable unsaturated group in the fluorine-containing polymerizable resin of the present invention is such that the radically polymerizable unsaturated group equivalent is 250 to 500 g / eq. The ratio is preferably from the viewpoint of excellent antifouling properties of the cured coating film, particularly 300 to 400 g / eq. It is particularly preferable that the range is

  The fluorine-containing polymerizable resin of the present invention can itself be used as the main component of the active energy ray-curable composition, but has an extremely excellent surface modification performance, so that the active energy ray-curable composition is used. By using as a fluorine-based surfactant or fluorine-based surface modifier to be added to the surface, excellent antifouling properties and slipperiness can be imparted to the cured coating film.

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

  The active energy ray-curable resin (D) 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, heptamethylene diisocyanate, octamethylene diisocyanate, decamethylene diisocyanate, 2-methyl-1,5-pentane diisocyanate, 3-methyl- 1,5-pentane diisocyanate, dodecamethylene diisocyanate, 2-methylpentamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, isophorone diisocyanate, norbornane diisocyanate, hydrogenated diphenylmethane diisocyanate , Hydrogenated tolylene diisocyanate, hydrogenated xylile Examples include diisocyanate, hydrogenated tetramethylxylylene diisocyanate, cyclohexyl diisocyanate, and the aromatic polyisocyanate compound includes tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, xylylene diisocyanate, 1,5-naphthalene diisocyanate, Examples include toridine diisocyanate and p-phenylene diisocyanate.

  On the other hand, examples of the 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 (E) 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 (E) can be used alone or in combination of two or more.

  In the active energy ray-curable composition of the present invention, when the fluorine-containing polymerizable resin of the present invention is used as a fluorine-containing surfactant or a fluorine-based surface modifier, the antifouling property and slipperiness are sufficient. Therefore, the amount used is in the range of 0.01 to 10 parts by mass with respect to 100 parts by mass in total of the active energy ray-curable resin (D) and the active energy ray-curable monomer (E). It is preferable that the range is 0.1 to 5% by mass.

  The fluorine-containing polymerizable resin or active energy ray-curable composition of the present invention can be formed into a cured coating film by irradiating active energy rays after being applied to a substrate. The active energy rays refer to ionizing radiation such as ultraviolet rays, electron beams, α rays, β rays, and γ rays. When a cured coating film is formed by irradiating ultraviolet rays as active energy rays, a photopolymerization initiator (F) is added to the fluorine-containing polymerizable resin or active energy ray curable composition to improve curability. It is preferable. Further, if necessary, a photosensitizer can be further added to improve curability. On the other hand, when ionizing radiation such as electron beam, α-ray, β-ray, and γ-ray is used, it cures quickly without using a photopolymerization initiator or photosensitizer. F) or a photosensitizer need not be added.

  Examples of the photopolymerization initiator (F) 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 (F), the compatibility with the active energy ray curable resin (D) and the active energy ray curable monomer (E) 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 (F) 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 rays for curing the active energy ray-curable composition of the present invention are ionizing radiations such as ultraviolet rays, electron beams, α rays, β rays, and γ rays. Or as a curing device, for example, a germicidal lamp, an ultraviolet fluorescent lamp, a carbon arc, a xenon lamp, a high-pressure mercury lamp for copying, a medium or high-pressure mercury lamp, an ultra-high pressure mercury lamp, an electrodeless lamp, a metal halide lamp, natural light, etc. Examples of the electron beam include ultraviolet rays, a scanning type, and a curtain type electron beam accelerator.

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

  The application method of the active energy ray-curable 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 cured coating film of the fluorine-containing polymerizable resin of the present invention has excellent antifouling properties (ink repellency, fingerprint resistance, etc.), scratch resistance, etc. It is possible to impart antifouling properties and slipperiness to the surface. In addition, since the fluorine-containing polymerizable resin of the present invention can add leveling properties to the coating material by adding it as a fluorine-based surfactant or a fluorine-based surface modifier to the coating material, The active energy ray curing agent composition has high leveling properties.

  As an article that can impart antifouling property and slipperiness to the surface using the fluorine-containing polymerizable resin or active energy ray-curable composition of the present invention, a film for polarizing plate of a liquid crystal display (LCD) such as a TAC film 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; transfer film for insert mold (IMD, IMF) Rubber rollers for office machines such as copiers and printers; glass surfaces of reading parts of office machines such as copiers and scanners; optical lenses such as cameras, video cameras and glasses; windshields of watches and watches such as watches; glass surfaces; , Windows for various vehicles such as railway vehicles; various building materials such as decorative panels; window glass for houses Woodworking materials such as furniture, 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 polymerizable resin or active energy ray-curable composition of the present invention to the surface of these articles and irradiating active energy rays such as ultraviolet rays to form a cured coating film, antifouling properties are formed on the article surfaces. And slipperiness can be imparted. Moreover, it is also possible to add antifouling property and slipperiness to the article surface by adding the fluorine-containing polymerizable resin of the present invention to various paints suitable for each article, and applying and drying.

  In addition, the coating material in which the fluorine-containing polymerizable resin of the present invention is added to the active energy ray-curable composition improves leveling properties, and also provides antifouling properties (ink repellency) and slipping properties (scratch resistance) on the coating film surface. Property). Examples of such a coating material include a hard coat material for an LCD polarizing plate such as a TAC film, an anti-glare (AG) anti-glare coating material, or an anti-reflection (LR) coating material; a plasma display (PDP), and an organic EL display. Hard coat materials for various display screens, etc .; hard coat materials for touch panels; RGB used in color filters (hereinafter referred to as “CF”) used in image sensors such as liquid crystal displays, organic EL displays, CCDs, and CMOSs. Color resist, printing ink, inkjet ink or paint for forming each pixel of the above; Black resist for CF black matrix, printing ink, inkjet ink or paint; For pixel partition such as plasma display (PDP), organic EL display Resin composition; Paint or hard coat material for mobile phone casing; hard coat material for mobile phone screen; hard coat material for optical recording media such as CD, DVD, Blu-ray disc; hard coat material for transfer film for insert mold (IMD, IMF) ; Coating materials for rubber rollers for OA equipment such as copiers and printers; Coating materials for glass for reading parts of OA equipment such as copying machines and scanners; Coating materials for optical lenses such as cameras, video cameras and glasses; Windshields for watches, glass coating materials; window coating materials for various vehicles such as automobiles and railway vehicles; printing inks or paints for various building materials such as decorative boards; coating materials for window glass for houses; Artificial / synthetic leather coating materials; paints or coating materials for various plastic molded products such as housings for home appliances; FRP bath paints or coatings And the like.

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

  Further, since the cured coating film of the fluorine-containing polymerizable 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 polymerizable 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 polymerizable resin or active energy ray-curable composition of the present invention can be used, optical fiber cladding materials, waveguides, liquid crystal panel sealing materials, various optical sealing materials, optical Adhesives and the like.

  In particular, when the active energy ray-curable 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 resin Excellent anti-glare properties by blending inorganic or organic fine particles such as fine particles at a ratio of 0.1 to 0.5 times the total mass of the curing component in the active energy ray-curable composition of the present invention. Since it becomes a thing, it is preferable.

  In addition, when the fluorine-containing polymerizable resin or active energy ray-curable composition of the present invention is used for an antiglare coating material for a protective film of a polarizing plate for LCD, it is applied to a mold having an uneven surface shape before the coating material is cured. After the contact, it can be applied to a transfer method in which an active energy ray is irradiated and cured from the side opposite to the mold, and the surface of the coating film is embossed to impart an antiglare property. In addition, a transfer method in which the surface of the coating film is mirrored by irradiating with an active energy ray from the opposite side of the mold or film after contacting the mold or film having a mirror surface before curing the coating material. It can also be applied to.

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

[IR spectrum measurement method]
Using a measuring device of “IR Prestige-21” manufactured by Shimadzu Corporation, a small amount of the sample solution was dropped on the KBr plate and the solvent was dried, and then the measurement was performed.

[GPC measurement conditions]
Measuring device: “HLC-8220 GPC” manufactured by Tosoh Corporation
Column: Guard column “HHR-H” manufactured by Tosoh Corporation (6.0 mm ID × 4 cm)
+ "TSK-GEL GMHHR-N" (7.8 mm ID x 30 cm) manufactured by Tosoh Corporation
+ "TSK-GEL GMHHR-N" (7.8 mm ID x 30 cm) manufactured by Tosoh Corporation
+ "TSK-GEL GMHHR-N" (7.8 mm ID x 30 cm) manufactured by Tosoh Corporation
+ "TSK-GEL GMHHR-N" (7.8 mm ID x 30 cm) manufactured by Tosoh Corporation
Detector: ELSD ("ELSD2000" manufactured by Oltec)
Data processing: “GPC-8020 Model II data analysis version 4.30” manufactured by Tosoh Corporation
Measurement conditions: Column temperature 40 ° C
Developing solvent Tetrahydrofuran (THF)
Flow rate 1.0 ml / min Sample: A 1.0% by mass tetrahydrofuran solution filtered in terms of resin solids through a microfilter (100 μl).
Standard sample: The following monodisperse polystyrene having a known molecular weight was used in accordance with the measurement manual of “GPC-8020 Model II Data Analysis Version 4.30”.

(Monodispersed polystyrene)
“A-500” manufactured by Tosoh Corporation
"A-1000" manufactured by Tosoh Corporation
"A-2500" manufactured by Tosoh Corporation
"A-5000" manufactured by Tosoh Corporation
“F-1” manufactured by Tosoh Corporation
"F-2" manufactured by Tosoh Corporation
“F-4” manufactured by Tosoh Corporation
“F-10” manufactured by Tosoh Corporation
“F-20” manufactured by Tosoh Corporation
“F-40” manufactured by Tosoh Corporation
“F-80” manufactured by Tosoh Corporation
“F-128” manufactured by Tosoh Corporation
“F-288” manufactured by Tosoh Corporation
“F-550” manufactured by Tosoh Corporation

(Synthesis Example 1)
A glass flask equipped with a stirrer, a thermometer, a condenser, and a dropping device has a poly (perfluoroalkylene ether) chain represented by the following formula (a2-1-1), and has hydroxyl groups at both ends. 20 parts by mass of a compound, 10 parts by mass of metaxylene hexafluoride as a solvent, 0.02 parts by mass of p-methoxyphenol as a polymerization inhibitor, and 1.5 parts by mass of triethylamine as a neutralizing agent are stirred in an air stream. Then, 1.3 parts by mass of methacrylic acid chloride was added dropwise over 1 hour while maintaining the inside of the flask at 10 ° C. After completion of dropping, the mixture was stirred at 10 ° C. for 1 hour, heated, stirred at 30 ° C. for 1 hour, further heated to 50 ° C. and stirred for 10 hours, and then disappearance of methacrylic acid chloride by gas chromatography measurement. The reaction was terminated. Next, after adding 70 parts by mass of meta-xylene hexafluoride as a solvent, 80 parts by mass of ion-exchanged water was mixed and stirred, and then allowed to stand, and washing by a method of separating and removing the aqueous layer was repeated three times. Subsequently, 0.02 parts by mass of p-methoxyphenol was added as a polymerization inhibitor, 8 parts by mass of magnesium sulfate was added as a dehydrating agent, and the mixture was allowed to stand for 1 day for complete dehydration, and then the dehydrating agent was filtered off. .

（式中、ｐは平均１７、ｑは平均１９であり、ポリ（パーフルオロアルキレンエーテル）鎖部分の平均分子量は３，４４２である。なお、オキシパーフルオロメチレン単位とオキシパーフルオロエチレン単位との結合はランダムである。以下同じ。）

(Wherein p is an average of 17 and q is an average of 19 and the average molecular weight of the poly (perfluoroalkylene ether) chain portion is 3,442. It should be noted that the oxyperfluoromethylene unit and the oxyperfluoroethylene unit are (The bond is random. The same applies hereinafter.)

  Subsequently, the solvent was distilled off under reduced pressure to obtain a compound represented by the following formula (A-2-1) (hereinafter abbreviated as “compound (A-2-1)”).

(Synthesis Example 2)
A glass flask equipped with a stirrer, thermometer, condenser, and dropping device has a poly (perfluoroalkylene ether) chain represented by the above formula (a2-1-1), and has hydroxyl groups at both ends. 20 parts by mass of a compound and 0.006 parts by mass of p-methoxyphenol as a polymerization inhibitor were added, stirring was started under an air stream, and 1.5 parts by mass of 2-methacryloyloxyethyl isocyanate while maintaining the inside of the flask at 60 ° C. Was added dropwise over 1 hour. After completion of the dropwise addition, the mixture was stirred at 60 ° C. for 2 hours, heated up and stirred at 80 ° C. for 4 hours. After confirming the disappearance of 2-methacryloyloxyethyl isocyanate by gas chromatography measurement, the reaction was terminated. A compound represented by the formula (A-6-1) (hereinafter abbreviated as “compound (A-6-1)”) was obtained.

(Synthesis Example 3)
A compound having a poly (perfluoroalkylene ether) chain represented by the following formula (a2 ′) in a glass flask equipped with a stirrer, a thermometer, a condenser, and a dropping device, and having a hydroxyl group at both ends thereof 20 mass Parts, 20 parts by mass of diisopropyl ether as a solvent, 0.02 parts by mass of p-methoxyphenol as a polymerization inhibitor and 3.1 parts by mass of triethylamine as a neutralizing agent, stirring was started under an air stream, While maintaining the temperature at 10 ° C., 2.7 parts by mass of acrylic acid chloride was added dropwise over 1 hour. After completion of dropping, the mixture was stirred at 10 ° C. for 1 hour, heated, stirred at 30 ° C. for 1 hour, further heated to 50 ° C. and stirred for 10 hours, and then disappearance of acrylic acid chloride by gas chromatography measurement. The reaction was terminated. Next, after adding 70 parts by mass of diisopropyl ether as a solvent, 80 parts by mass of ion-exchanged water was mixed, stirred, and allowed to stand, and washing by a method of separating and removing the aqueous layer was repeated three times. Subsequently, 0.02 parts by mass of p-methoxyphenol was added as a polymerization inhibitor, 8 parts by mass of magnesium sulfate was added as a dehydrating agent, and the mixture was allowed to stand for 1 day for complete dehydration, and then the dehydrating agent was filtered off. .

（式中、ｒは平均５、ｓは平均８であり、ポリ（パーフルオロアルキレンエーテル）鎖部分の平均分子量は１，３７４である。なお、パーフルオロメチレン構造とパーフルオロエチレン構造との結合はランダムである。以下同じ。）

(Wherein, r is 5 on average, s is 8 on average, and the average molecular weight of the poly (perfluoroalkylene ether) chain portion is 1,374. Note that the bond between the perfluoromethylene structure and the perfluoroethylene structure is Random. The same shall apply hereinafter.)

  Subsequently, the solvent was distilled off under reduced pressure to obtain a compound represented by the following formula (A ′) (hereinafter abbreviated as “compound (A ′)”).

Example 1
A glass flask equipped with a stirrer, a thermometer, a condenser, and a dropping device was charged with 146.1 parts by mass of metaxylene hexafluoride as a solvent, and the temperature was raised to 105 ° C. while stirring in a nitrogen stream. Next, 83.5 parts by mass of the compound (A-2-1) obtained in Synthesis Example 1, 160 parts by mass of 2-hydroxyethyl methacrylate (hereinafter abbreviated as “HEMA”), and a radical polymerization initiator Three types of dripping liquid with a polymerization initiator solution in which 36.5 parts by mass of t-butylperoxy-2-ethylhexanoate was dissolved in 306.2 parts by mass of metaxylene hexafluoride 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 5 hours.

Next, 0.17 parts by mass of p-methoxyphenol as a polymerization inhibitor and 0.13 parts by mass of tin octylate as a urethanization catalyst were added, stirring was started under an air stream, and 2-acryloyloxy was maintained while maintaining 60 ° C. 169.9 parts by mass of ethyl isocyanate (hereinafter abbreviated as “AOI”) was added dropwise over 1 hour. After completion of dropping, the mixture was stirred at 60 ° C. for 2 hours, further heated to 80 ° C. and stirred for 4 hours, and then the disappearance of an absorption peak near 2360 cm ⁻¹ derived from isocyanate groups was confirmed by IR spectrum measurement. Subsequently, metaxylene hexafluoride was added to obtain metaxylene hexafluoride containing 50% by mass of the fluorine-containing polymerizable resin (1). As a result of measuring the molecular weight of the obtained fluorine-containing polymerizable resin (1) by GPC (polystyrene conversion molecular weight), it was a number average molecular weight 1,200 and a weight average molecular weight 6,300. The fluorine content was 12% by mass. An IR spectrum chart of the fluorine-containing polymerizable resin (1) is shown in FIG. 1, and a GPC chart is shown in FIG.

(Example 2)
A glass flask equipped with a stirrer, a thermometer, a condenser, and a dropping device was charged with 146.1 parts by mass of metaxylene hexafluoride as a solvent, and the temperature was raised to 105 ° C. while stirring in a nitrogen stream. Next, 83.5 parts by mass of the compound (A-6-1) obtained in Synthesis Example 2, 160 parts by mass of HEMA, and 36.5 parts by mass of t-butylperoxy-2-ethylhexanoate as a radical polymerization initiator. 3 parts of the dropping solution with a polymerization initiator solution dissolved in 306.2 parts by weight of metaxylene hexafluoride was set in separate dropping devices, and dropped simultaneously over 2 hours while keeping the flask at 105 ° C. did. After completion of dropping, the mixture was stirred at 105 ° C. for 5 hours.

Next, 0.17 parts by mass of p-methoxyphenol as a polymerization inhibitor and 0.13 parts by mass of tin octylate as a urethanization catalyst were charged, stirring was started under an air stream, and AOI 169.9 was maintained at 60 ° C. Part by mass was added dropwise over 1 hour. After completion of dropping, the mixture was stirred at 60 ° C. for 2 hours, further heated to 80 ° C. and stirred for 4 hours, and then the disappearance of an absorption peak near 2360 cm ⁻¹ derived from isocyanate groups was confirmed by IR spectrum measurement. Subsequently, metaxylene hexafluoride was added to obtain metaxylene hexafluoride containing 50% by mass of the fluorine-containing polymerizable resin (2). As a result of measuring the molecular weight of the obtained fluorine-containing polymerizable resin (2) by GPC (polystyrene equivalent molecular weight), it was a number average molecular weight 1,300 and a weight average molecular weight 2,800. The fluorine content was 12% by mass. In addition, the chart figure of IR spectrum of fluorine-containing polymeric resin (2) is shown in FIG. 1, and the chart figure of GPC is shown in FIG.

(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. Next, 137.8 parts by mass of a monomer solution obtained by dissolving 40 parts by mass of a fluorinated alkyl group-containing acrylate represented by the following formula (Y) and 28.8 parts by mass of HEMA in 69 parts by mass of methyl isobutyl ketone, and a radical polymerization initiator 2 drops of a polymerization initiator solution obtained by dissolving 3.4 parts by mass of t-butylperoxy-2-ethylhexanoate in 22.5 parts by mass of methyl isobutyl ketone It set to the apparatus and it was dripped over 3 hours simultaneously, keeping the inside of a flask at 105 degreeC. After completion of dropping, the mixture was stirred at 105 ° C. for 10 hours to obtain a polymer.

Next, 0.1 parts by mass of p-methoxyphenol as a polymerization inhibitor and 0.05 parts by mass of dibutyltin dilaurate as a urethanization catalyst were charged, and 31.2 parts by mass of AOI was maintained in 1 hour while maintaining 60 ° C. in an air stream. It was dripped. After completion of the dropwise addition, the mixture was stirred at 60 ° C. for 1 hour, then heated to 80 ° C. and stirred for 10 hours, whereby the disappearance of the absorption peak near 2360 cm ⁻¹ derived from isocyanate groups 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 fluorine-containing polymerizable resin (3). As a result of measuring the molecular weight of the fluorine-containing polymerizable resin (3) by GPC (polystyrene equivalent molecular weight), the number average molecular weight was 3,000 and the weight average molecular weight was 7,000. The fluorine content was 20% by mass.

(Comparative Example 2)
A glass flask equipped with a stirrer, thermometer, condenser, and dropping device was charged with 63 parts by mass of methyl isobutyl ketone as a solvent and heated to 105 ° C. while stirring under a nitrogen stream. Next, 21.5 parts by mass of the compound (A ′) obtained in Synthesis Example 3, 41.3 parts by mass of HEMA, and 9.4 parts by mass of t-butylperoxy-2-ethylhexanoate as a radical polymerization initiator 3 types of dripping liquid and 135.4 parts by mass of a polymerization initiator solution dissolved in 126 parts by mass of methyl isobutyl ketone were set in separate dripping apparatuses, respectively, and dripped simultaneously over 2 hours while keeping the inside of the flask at 105 ° C. did. After completion of dropping, the mixture was stirred at 105 ° C. for 10 hours, and then a part of the solvent was distilled off under reduced pressure to obtain a polymer.

Next, 74.7 parts by mass of methyl ethyl ketone, 0.1 part by mass of p-methoxyphenol as a polymerization inhibitor, and 0.06 part by mass of dibutyltin dilaurate as a urethanization catalyst were added, and stirring was started under an air stream. While maintaining, 44.8 parts by mass of AOI was added dropwise over 1 hour. After completion of the dropwise addition, the mixture was stirred at 60 ° C. for 1 hour, then heated to 80 ° C. and stirred for 10 hours to confirm the disappearance of the absorption peak near 2360 cm ⁻¹ derived from the isocyanate group by IR spectrum measurement. A methyl ethyl ketone solution containing 50% by mass of the fluoropolymer resin (4) was obtained. As a result of measuring the molecular weight of the obtained fluorine-containing polymerizable resin (4) by GPC (polystyrene equivalent molecular weight), it was a number average molecular weight 2,400 and a weight average molecular weight 7,100. The fluorine content was 11% by mass.

[Preparation of base composition of active energy ray-curable composition for evaluation]
50 parts by mass of pentafunctional non-yellowing urethane acrylate, 50 parts by mass of dipentaerythritol hexaacrylate, 25 parts by mass of butyl acetate, photopolymerization initiator (“IRGACURE 184” manufactured by BASF Japan Ltd .; 1-hydroxycyclohexyl phenyl ketone) Parts, toluene 54 parts by weight, 2-propanol 28 parts by weight, ethyl acetate 28 parts by weight and propylene glycol monomethyl ether 28 parts by weight are mixed uniformly, and the base composition 268 of the active energy ray-curable composition for evaluation is mixed. A mass part was obtained.

(Examples 3 and 4, Comparative Examples 3 to 5)
50 mass% of the fluorine-containing polymerizable resins (1) to (4) obtained in Examples 1 and 2 and Comparative Examples 1 and 2 as fluorine-containing surfactants in 268 parts by mass of the base composition obtained above. 2 parts by mass of each solution (1 part by mass as a resin component) was added and mixed uniformly to obtain an active energy ray-curable composition. Subsequently, this active energy ray-curable composition was applied to bar coater No. 13 was applied to a polyethylene terephthalate (PET) film having a thickness of 188 μm, and then placed in a dryer at 60 ° C. for 5 minutes to volatilize the solvent. Next, the dried coating film was cured by irradiating with ultraviolet rays (UV) with an ultraviolet curing device (under a nitrogen atmosphere (oxygen concentration of 1% by volume or less), a high-pressure mercury lamp, and an ultraviolet irradiation amount of ² kJ / m ² ). 4 and Comparative Examples 3 and 4 were prepared as coated films. Moreover, the coating film was similarly produced about only the base composition of the active energy ray hardening-type composition, without adding anything, and it was set as the comparative example 5.

(Evaluation of antifouling properties)
The antifouling property of the coated surface of the coated film obtained above was evaluated from the following contact angles of water and n-dodecane, stain adhesion preventing property, and stain wiping ease.

[Measurement of contact angle of water and n-dodecane]
About the coating surface of the coating film, the contact angle of water and n-dodecane was measured using the contact angle measuring apparatus (Kyowa Interface Science Co., Ltd. "MODEL CA-W150").

[Evaluation of antifouling properties after wear treatment]
As an evaluation of antifouling durability, the contact angles of water and n-dodecane were measured in the same manner as described above for the coated film whose surface was subjected to abrasion treatment. The wear treatment was performed by attaching a non-woven fabric (“Bencot S” manufactured by Asahi Kasei Fibers Co., Ltd.) to a jig using a reciprocating wear tester (“HEIDON Tribogear TYPE: 30S” manufactured by Shinto Kagaku Co., Ltd.) of 1.72N. It was performed by carrying out 5000 round-trip wear with a load of / cm ² .

[Evaluation of dirt adhesion prevention]
On the coated surface of the coated film, a line was drawn with a felt pen (magic ink large black made by Teranishi Chemical Co., Ltd.), and the adhesion of the black ink was visually observed to evaluate the antifouling property. . The evaluation criteria are as follows.
AA: The antifouling property is the best and the ink repels.
A: The ink does not repel and forms a linear repelling (the line width is less than 50% of the width of the tip of the felt pen).
B: 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.
C: The ink can be drawn cleanly on the surface without repelling at all.

[Evaluation of ease of wiping off dirt]
After the above test for preventing soil adhesion, the number of times of wiping required to wipe all the adhered ink with a tissue paper at a load of 500 g was measured. From the results, the ease of soil wiping was evaluated according to the following criteria.
AA: The ink can be completely removed by wiping once.
A: The ink was completely removed by wiping 2 to 5 times.
B: The ink was completely removed by wiping 6 to 10 times.
C: The ink could not be completely removed by 10 wiping operations.

(Evaluation of slipperiness)
Using a surface property measuring instrument ("HEIDON-14D" manufactured by Shinto Kagaku Co., Ltd.), after fixing the sample on the sample table and checking the level, set the probe on the sample and rub any distance with a load of 100g A stable portion of the obtained chart was sampled to calculate a dynamic friction coefficient.

  The measurement and evaluation results are shown in Table 1.

  Curing of the active energy ray-curable coating compositions of Examples 3 and 4 to which the fluorine-containing curable resins (1) and (2) obtained in Examples 1 and 2 which are fluorine-containing polymerizable resins of the present invention were added. The coating film was found to have a high contact angle of water and n-dodecane. It was also found that the contact angles of water and n-dodecane did not greatly decrease after the abrasion treatment, and the antifouling durability was high. It was also found that the anti-smudge property was high and the ease of wiping off the soil was high. Furthermore, it was found that the coefficient of dynamic friction was low and the slipperiness was excellent.

  On the other hand, Comparative Example 3 using the fluorine-containing curable resin (3) having a perfluoroalkyl group introduced in place of the poly (perfluoroalkylene ether) chain produced in Comparative Example 1 has a water contact angle of less than 100 °. It was found that the water repellency was insufficient and both the contact angle of water and the contact angle of n-dodecane were greatly reduced after the abrasion treatment. Moreover, although it had comparatively good dirt adhesion prevention property, it was found that the dirt wiping ease was insufficient, the dynamic friction coefficient was high, and the slipperiness was insufficient.

  Fluorine-containing curable resin (4) using as a raw material a compound having an acryloyl group at both ends of a poly (perfluoroalkylene ether) chain having a lower molecular weight than that used in the fluorine-containing polymerizable resin of the present invention produced in Comparative Example 2 In Comparative Example 4 using), the contact angle of water and n-dodecane was high, but it was found that both the contact angle of water and the contact angle of n-dodecane greatly decreased after the abrasion treatment. Further, the anti-smudge property was good, but the ease of wiping off the soil was somewhat low, the coefficient of dynamic friction was somewhat high, and the slipperiness was not satisfactory.

  It was found that Comparative Example 5 in which no additive was added had a low contact angle of water and n-dodecane, and was inferior in dirt adhesion prevention, dirt wiping ease and slipperiness.

Claims (5)

Compound average molecular weight of 3, 0 00-4 5 00 a is poly (perfluoroalkylene ether) having a chain having a radical polymerizable unsaturated group at both ends and (A), the reactive group (b) A polymer (P) obtained by copolymerizing a radically polymerizable unsaturated monomer (B) having an essential monomer component in a fluorine-based solvent as an essential monomer component and reacting with the reactive group (b). A fluorine-containing polymerizable resin obtained by reacting a compound (C) having a functional group (c) having a radical polymerizable unsaturated group,
The monomer (B) has a radically polymerizable unsaturated monomer having at least one reactive group selected from the group consisting of a hydroxyl group, an isocyanate group, an epoxy group and a carboxyl group, or a radically polymerizable unsaturated group A carboxylic acid halide or a carboxylic acid anhydride,
The compound (C) is a compound having at least one functional group selected from the group consisting of a hydroxyl group, an isocyanate group, an epoxy group and a carboxyl group and a radical polymerizable unsaturated group, or a carboxylic acid having a radical polymerizable unsaturated group A fluorine-containing polymerizable resin, which is a halide or a carboxylic acid anhydride.   2. The fluorine-containing compound according to claim 1, wherein the reactive functional group (b) of the radical polymerizable monomer (B) is a hydroxyl group and the functional group (c) of the compound (C) is an isocyanate group. Polymerizable resin. The claim 1 or 2 Symbol placement of the fluoropolymer resin, applied to the substrate, the cured product characterized by being formed by curing by an active energy ray. Claim 1 or 2 Symbol placement of the fluoropolymer resin, and active energy ray curable type is characterized by containing a radiation-curable resin (D) or an active energy ray-curable monomer (E) Composition. A cured product obtained by applying the active energy ray-curable composition according to claim 4 to a substrate and irradiating and curing the active energy ray.

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