JP2012246389A - Polymerizable fluorine surface-modified silica particle and active energy ray curable composition using the same - Google Patents

Abstract

Disclosed is a polymerizable fluorine surface-modified silica particle which is an additive capable of imparting excellent antifouling properties to a coating film surface even when added in a small amount. Moreover, the active energy ray-curable composition containing the said silica particle, the hardened | cured material, and the articles | goods which have the cured coating film are provided.
A poly (perfluoroalkylene ether) chain, a compound (A) having a polymerizable unsaturated group at both ends thereof, a polymerizable unsaturated monomer (B) having a reactive functional group (b), and The surface-modified silica particles (P) obtained by polymerizing silica particles (C) having a polymerizable unsaturated group as essential components are functional groups (d) having reactivity with the functional groups (b). And polymerizable fluorine surface-modified silica particles obtained by reacting the compound (D) having a polymerizable unsaturated group and an active energy ray-curable composition containing the silica particles.
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Description

  The present invention relates to polymerizable fluorine surface-modified silica particles modified with a fluorine-containing resin having a polymerizable unsaturated group on the surface of silica particles. The present invention also relates to an active energy ray-curable composition using the silica particles, a cured product thereof, and an article having the cured coating film.

  The fluorine-containing compound has both water repellency and oil repellency, and can impart water repellency and oil repellency by coating on the surface of the article. Therefore, the fluorine-containing compound is used for the purpose of imparting antifouling properties to the outermost surface of display screens of various flat panel displays such as liquid crystal displays, plasma displays, and organic EL displays.

  Here, a particular problem in the display screens of various flat panel displays is dirt such as fingerprints, and when this dirt adheres, there is a problem that the display becomes difficult to see. In particular, in touch panels that use display screens such as mobile phones, smartphones, tablet PCs, car navigation systems, etc. that frequently touch the skin and fingers, and operation panels of various devices as operation panels, fingerprints and other stains Prevention of adhesion, that is, antifouling property is required.

  Poly (perfluoro) produced from a compound having a (perfluoroalkylene ether) chain and a di (meth) acryloyl group at both ends as a material for imparting antifouling properties to display screens of various flat panel displays A fluorine-containing radical polymerizable resin having an (alkylene ether) chain and an unsaturated group has been proposed (see, for example, Patent Document 1). The fluorine-containing radical polymerizable resin can impart high antifouling properties to the cured coating film when added to a coating material.

  Generally, when an antifouling property is imparted by adding an additive to a coating material, a sufficient antifouling property cannot be exhibited unless an addition amount of a certain amount or more is added. However, there was a problem that the original physical properties of the coating material were impaired as the amount added increased. The fluorine-containing radically polymerizable resin described in Patent Document 1 also has a problem that sufficient antifouling properties cannot be exhibited by adding a very small amount. Accordingly, an antifouling agent that exhibits excellent antifouling properties in a smaller amount has been demanded.

International Publication WO2009 / 133770

  The problem to be solved by the present invention is to provide polymerizable fluorine surface-modified silica particles, which are additives that can impart excellent antifouling properties to the coating surface even when added in a small amount. Moreover, it is providing the article | item which has the active energy ray-curable composition containing the said silica particle, its hardened | cured material, and its hardened coating film.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have obtained a poly (perfluoroalkylene ether) chain, a compound having a polymerizable unsaturated group at both ends thereof, and a polymerizable having a reactive functional group. A surface-modified silica particle obtained by polymerizing an unsaturated monomer and a silica particle having a polymerizable unsaturated group has a functional group and a polymerizable unsaturated group reactive to the reactive functional group. The active energy ray-curable composition containing polymerizable fluorine surface-modified silica particles obtained by reacting a compound having a compound, even if the addition of the polymerizable fluorine surface-modified silica particles to the composition is very small, It discovered that the antifouling property outstanding on the cured coating film surface of this composition could be provided, and completed this invention.

  That is, the present invention relates to a compound (A) having a poly (perfluoroalkylene ether) chain and a polymerizable unsaturated group at both ends thereof, a hydroxyl group, an isocyanate group, an epoxy group, a carboxyl group, an acid anhydride group, and a carboxylic acid. Polymerizing as an essential component a polymerizable unsaturated monomer (B) having at least one functional group (b) selected from the group consisting of halide groups and silica particles (C) having a polymerizable unsaturated group. The resulting surface-modified silica particles (P) are reactive with respect to the functional group (b) and are composed of a hydroxyl group, an isocyanate group, an epoxy group, a carboxyl group, an acid anhydride group, and a carboxylic acid halide group. Polymerizable fluorine surface-modified silica particles obtained by reacting a compound (D) having at least one functional group (d) and a polymerizable unsaturated group selected from To the active energy ray-curable composition containing particles.

  Furthermore, the present invention has a cured product obtained by applying the active energy ray-curable composition to a substrate and irradiating and curing the active energy ray, and a cured coating film of the active energy ray-curable composition. It relates to goods.

  The polymerizable fluorine surface-modified silica particles of the present invention can be used as an additive (antifouling agent) that imparts excellent antifouling properties, and the cured coating film can be added to various paints and coating materials with a very small amount of addition. Excellent antifouling properties can be imparted. In particular, since the polymerizable fluorine surface-modified silica particles of the present invention have a polymerizable unsaturated group, the silica particles are shared in the resin matrix by irradiation with active energy rays when added to the active energy ray-curable composition. Since it is fixed by bonding, its antifouling property changes little with time.

  Therefore, the polymerizable fluorine surface-modified silica particles of the present invention are very effective when it is desired to provide excellent antifouling properties while suppressing deterioration of the original properties of various paints and coating materials due to the addition of additives. is there.

1 is an observation photograph of the polymerizable fluorine surface-modified silica particles (1) obtained in Example 1 at a magnification of 100,000 times by a field emission scanning electron microscope (FE-SEM). FIG. 2 is an observation photograph of the silica particles having a polymerizable unsaturated group used as a raw material in Example 1 at a magnification of 100,000 with a field emission scanning electron microscope (FE-SEM).

  The polymerizable fluorine surface-modified silica particles of the present invention comprise a poly (perfluoroalkylene ether) chain and a compound (A) having a polymerizable unsaturated group at both ends thereof, a hydroxyl group, an isocyanate group, an epoxy group, a carboxyl group, an acid. A polymerizable unsaturated monomer (B) having at least one functional group (b) selected from the group consisting of an anhydride group and a carboxylic acid halide group, and silica particles (C) having a polymerizable unsaturated group. The surface-modified silica particles (P) obtained by polymerizing as an essential component have reactivity with the functional group (b) and have a hydroxyl group, an isocyanate group, an epoxy group, a carboxyl group, an acid anhydride group, and a carboxyl group. It is obtained by reacting a compound (D) having at least one functional group (d) selected from the group consisting of acid halide groups and a polymerizable unsaturated group.

  The compound (A) having a poly (perfluoroalkylene ether) chain and a polymerizable unsaturated group at both ends thereof as a raw material for the polymerizable fluorine surface-modified silica particles of the present invention will be described below.

Examples of the poly (perfluoroalkylene ether) chain of the compound (A) include those having a structure in which divalent fluorocarbon groups having 1 to 3 carbon atoms and oxygen atoms are alternately connected. The divalent fluorocarbon group having 1 to 3 carbon atoms may be one kind or a mixture of plural kinds. Specifically, those represented by the following structural formula (a1) may be used. Can be mentioned.

(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 a block shape, and n is an integer of 1 or more representing a repeating unit.

  Among these, since the wiping property of dirt on the coating film surface is particularly good and a coating film having excellent antifouling properties is obtained, the perfluoromethylene structure represented by the structural formula (a1-1), Those coexisting with the perfluoroethylene structure represented by the structural 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 because the antifouling property is improved. Moreover, the value of n in the structural formula (a1) is preferably in the range of 3 to 100, and more preferably in the range of 6 to 70.

  The following general formulas (a2-1) to (a2-6) may be mentioned as the compound before introducing a polymerizable unsaturated group at both ends as a raw material of the compound (A). In the following structural formulas, “—PFPE—” represents the poly (perfluoroalkylene ether) chain.

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

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

  As the method for producing the compound (A), for example, a method of obtaining a compound having one hydroxyl group at both ends of a poly (perfluoroalkylene ether) chain by dehydrochlorination of (meth) acrylic acid chloride. , 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 with a compound having one carboxyl group at both ends of the chain; a method obtained by esterifying glycidyl (meth) acrylate; Perfluoroalkylene ether) isocyanate groups at both ends of the chain Relative to the compound having one, 2-hydroxyethyl (meth) method of introducing by reacting an acrylate, a method of reacting 2-hydroxyethyl (meth) 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 urethanization of oxyethyl isocyanate is particularly preferred because it is easily obtained synthetically.

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

  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, since the industrial production of the compound (A) itself is particularly easy and the polymerization reaction when producing the surface-modified silica particles (P) is also easy, the structural formula (A-1), Those represented by (A-2), (A-5), and (A-6) are preferred. Moreover, since chemical resistance improves, the said structural formula (A-2), (A-4), (A-12), (A-13) is preferable.

  Next, the polymerizable unsaturated monomer (B) having a functional group (b) as a raw material for the polymerizable fluorine surface-modified silica particles of the present invention will be described.

  The functional group (b) of the monomer (B) is at least one selected from the group consisting of a hydroxyl group, an isocyanate group, an epoxy group, a carboxyl group, an acid anhydride group, and a carboxylic acid halide group. The polymerizable unsaturated monomer (B) having these functional groups (b) may be used alone or in combination of two or more different functional groups (b). You can also

  Further, the polymerizable unsaturated group of the monomer (B) is preferably a group having a carbon-carbon unsaturated double bond having radical polymerizability, and more specifically, a (meth) acryloyl group, vinyl. Group, maleimide group, and the like. Among these, a (meth) acryloyl group is more preferable because polymerization with the compound (A) and silica particles (C) having a polymerizable unsaturated group described later is easy.

  Specific examples of the 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 (meth) acrylate, polypropylene Glycol mono (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2- (meth) acryloyloxyethyl-2-hydroxyethyl phthalate, lactone-modified (meth) acrylate having a hydroxyl group at the terminal Unsaturated monomer having a hydroxyl group such as relate; 2- (meth) acryloyloxyethyl isocyanate, 2- (2- (meth) acryloyloxyethoxy) ethyl isocyanate, 1,1-bis ((meth) acryloyloxymethyl) Unsaturated monomers having an isocyanate group such as ethyl isocyanate; unsaturated monomers having an epoxy group such as glycidyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate glycidyl ether; (meth) acrylic acid, 2- Unsaturated monomers having a carboxyl group such as (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl phthalic acid, maleic acid and itaconic acid; acid anhydride groups such as maleic anhydride and itaconic anhydride An unsaturated monomer having (meth) acrylic acid chloride (Meth) and the like unsaturated monomer having a carboxylic acid halide group such as acrylic acid bromide.

  Next, the silica particle (C) having a polymerizable unsaturated group that is a raw material of the polymerizable fluorine surface-modified silica particle of the present invention will be described.

  The silica particles (C) have a polymerizable unsaturated group on the surface thereof. The polymerizable unsaturated group is preferably a group having a carbon-carbon unsaturated double bond having radical polymerizability, more specifically, a (meth) acryloyl group, a vinyl group, a maleimide group, and the like. Among these, a (meth) acryloyl group is more preferable because polymerization with the compound (A) and the monomer (B) is easy.

  As a method for introducing a polymerizable unsaturated group into the surface of the silica particle (C), a silane compound having a functional group that reacts with silanol present on the surface of the silica particle and a polymerizable unsaturated group is reacted with the silica particle. A method is mentioned. Examples of the silane compound include vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, and 3-methacrylate. Examples include loxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, and 3-acryloxypropyltrimethoxysilane. Moreover, reaction with a silica particle and the said silane compound can be performed by a conventional method.

  Furthermore, the said silica particle (C) can also be obtained as a commercial item, For example, Nissan Chemical Industries Ltd. "MIBK-SD", "MIBK-SD-MS", "MIBK-SD-L", “MIBK-SD-ZL”; “DP1021”, “DP1022”, “DP1032”, “DP1037”, “DP1041”, “DP1042”, “DP1044” manufactured by JGC Catalysts & Chemicals Co., Ltd.

  The average particle diameter of the silica particles (C) is preferably in the range of 1 to 100 nm and more preferably in the range of 10 to 70 nm in order to maintain the transparency of the cured coating film of the active energy ray-curable composition described later. preferable. The average particle size can be measured using a particle size distribution meter using a laser Doppler method (for example, “Zeta potential / particle size measurement system ELSZ-2” manufactured by Otsuka Electronics Co., Ltd.).

  In producing the surface-modified silica particles (P), in addition to the compound (A), the monomer (B) and the silica particles (C), other polymerizable unsaturated monomers that can be copolymerized therewith. The body may be used. 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 Aromatic vinyls such as styrene, α-methylstyrene, p-methylstyrene, p-methoxystyrene; maleimide, methylmer Imides, ethylmaleimide, propyl maleimide, butyl maleimide, hexyl maleimide, octyl maleimide, dodecyl maleimide, stearyl maleimide, phenyl maleimide, and the like maleimides such as cyclohexyl maleimide.

  The method for producing the surface-modified silica particles (P) includes the step of mixing the compound (A), the monomer (B), the silica particles (C), and other polymerizable unsaturated monomers as necessary. And a method of copolymerization in the presence of a radical polymerization initiator. As the organic solvent used here, ketones, esters, amides, sulfoxides, ethers, hydrocarbons, and fluorine-based solvents are preferable. Specifically, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate Butyl acetate, propylene glycol monomethyl ether acetate, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, toluene, xylene, 1,3-bis (trifluoromethyl) benzene, 1,4-bis (trifluoromethyl) benzene and the like can be mentioned. These organic solvents are appropriately selected in consideration of the boiling point, compatibility with the raw material or polymer, and polymerizability. Moreover, since the compound (A) is particularly excellent in compatibility with an organic solvent, it is almost soluble in the organic solvent described above.

  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.

  The preparation ratio of the compound (A), the monomer (B), and the silica particles (C) when producing the surface-modified silica particles (P) is based on 1 part by mass of the silica particles (C). The total amount of the compound (A) and the monomer (B) is preferably in the range of 1 to 3 parts by mass, and more preferably in the range of 1.5 to 2.5 parts by mass.

  The surface-modified silica particles (P) obtained as described above are reacted with the functional group (d) having reactivity with the functional group (b) and the compound (D) having a polymerizable unsaturated group. Thus, the polymerizable fluorine surface-modified silica particles of the present invention can be obtained.

  The functional group (d) of the compound (D) is reactive from the functional group (b) and is selected from the group consisting of a hydroxyl group, an isocyanate group, an epoxy group, a carboxyl group, and a carboxylic acid halide group. At least one kind. When the functional group (b) is a hydroxyl group, the functional group (d) includes an isocyanate group, an epoxy group, a carboxyl group, an acid anhydride group, and a carboxylic acid halide group, and the functional group (b) is When the functional group (d) is an isocyanate group, a hydroxyl group is exemplified. When the functional group (b) is an epoxy group, the functional group (d) is a hydroxyl group, a carboxyl group, or an acid anhydride group. When the functional group (b) is a carboxyl group, examples of the functional group (c) include a hydroxyl group and an epoxy group. When the functional group (b) is a carboxylic acid halide group, Examples of the group (d) include a hydroxyl group. These may be a combination of a plurality of functional groups as long as the reaction is not hindered.

  Moreover, as a polymerizable unsaturated group which the said compound (D) has, the group which has a carbon-carbon unsaturated double bond which has radical polymerizability is preferable, More specifically, (meth) acryloyl group, vinyl group , Maleimide groups, and the like. Among these, the (meth) acryloyl group is more preferable because polymerization with the active energy ray curable resin (E) and the active energy ray curable monomer (F) described later is easy. preferable.

  Specific examples of the compound (D) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxy Butyl (meth) acrylate, 1,4-cyclohexanedimethanol mono (meth) acrylate, N- (2-hydroxyethyl) (meth) acrylamide, glycerin mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (Meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2- (meth) acryloyloxyethyl-2-hydroxyethyl phthalate, lactone-modified (meth) acrylate having a hydroxyl group at the terminal Unsaturated monomer having a hydroxyl group such as relate; 2- (meth) acryloyloxyethyl isocyanate, 2- (2- (meth) acryloyloxyethoxy) ethyl isocyanate, 1,1-bis ((meth) acryloyloxymethyl) Unsaturated monomers having an isocyanate group such as ethyl isocyanate; unsaturated monomers having an epoxy group such as glycidyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate glycidyl ether; (meth) acrylic acid, 2- Unsaturated monomers having a carboxyl group such as (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl phthalic acid, maleic acid and itaconic acid; acid anhydride groups such as maleic anhydride and itaconic anhydride An unsaturated monomer having (meth) acrylic acid chloride (Meth) and the like unsaturated monomer having a carboxylic acid halide group such as acrylic acid bromide. In addition, unsaturated monomers having a hydroxyl group and a plurality of polymerizable unsaturated groups such as 2-hydroxy-3-acryloyloxypropyl methacrylate, pentaerythritol triacrylate, and dipentaerythritol pentaacrylate can also be used.

  Among these, since polymerization curability by ultraviolet irradiation is particularly preferable, 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 surface-modified silica particles (P) with the functional group (d) having reactivity with the functional group (b) and the compound (D) having a polymerizable unsaturated group is the compound (C). The reaction may be performed under conditions in which the polymerizable unsaturated group therein does not polymerize. For example, the reaction is preferably carried out by adjusting the temperature condition in the range of 30 to 120 ° C. This reaction is preferably carried out in the presence of a catalyst or a polymerization inhibitor, and if necessary in the presence of an organic solvent.

  For example, when the functional group (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 temperature is 20 to 150 ° C., particularly 40 to 120 ° 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, or fluorine-based solvents, specifically acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, acetic acid. Ethyl, butyl acetate, propylene glycol monomethyl ether acetate, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, toluene, xylene, 1,3-bis (trifluoromethyl) benzene 1,4-bis (trifluoromethyl) benzene and the like. These may be appropriately selected in consideration of the boiling point and compatibility.

  The amount of the compound (D) used is preferably in the range of 1 to 1.5 mol with respect to 1 mol of the monomer (B) used as a raw material for the surface-modified silica particles (P). The range of -1.3 mol is more preferred.

  In addition, the fluorine content in the polymerizable fluorine surface-modified silica particles 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 5-40 mass% is more preferable, and the range of 10-35 mass% is further more preferable. The fluorine content in the polymerizable fluorine surface-modified silica particles of the present invention is a value calculated from the mass ratio of fluorine atoms to the total amount of raw materials used.

  The active energy ray-curable composition of the present invention is a blend of the polymerizable fluorine surface-modified silica particles of the present invention. The main component thereof is an active energy ray-curable resin (E) or an active energy ray. Contains a curable monomer (F). In the active energy ray-curable composition of the present invention, the active energy ray-curable resin (E) and the active energy ray-curable monomer (F) may be used alone or in combination. It doesn't matter.

  The active energy ray-curable resin (E) is a urethane (meth) acrylate resin, an unsaturated polyester resin, an epoxy (meth) acrylate resin, a polyester (meth) acrylate resin, an acrylic (meth) acrylate resin, or a resin having a maleimide group. However, urethane (meth) acrylate resin is preferable because of excellent transparency and low shrinkage.

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

  Examples of the aliphatic polyisocyanate compound include tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, octamethylene diisocyanate, decamethylene diisocyanate, 2-methyl-1,5-pentane diisocyanate, 3-methyl- 1,5-pentane diisocyanate, dodecamethylene diisocyanate, 2-methylpentamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, isophorone diisocyanate, norbornane diisocyanate, hydrogenated diphenylmethane diisocyanate , Hydrogenated tolylene diisocyanate, hydrogenated xylile Examples include diisocyanate, hydrogenated tetramethylxylylene diisocyanate, cyclohexyl diisocyanate, and the aromatic polyisocyanate compound includes tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, xylylene diisocyanate, 1,5-naphthalene diisocyanate, Examples include toridine diisocyanate and p-phenylene diisocyanate.

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

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

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

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

  Examples of the active energy ray-curable monomer (F) include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, and a number average molecular weight in the range of 150 to 1,000. Polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di having a number average molecular weight in the range of 150 to 1000 (Meth) acrylate, neopentyl glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol (Meth) acrylate, hydroxypivalate ester neopentyl glycol di (meth) acrylate, bisphenol A di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol Hexa (meth) acrylate, pentaerythritol tetra (meth) acrylate, trimethylolpropane di (meth) acrylate, dipentaerythritol penta (meth) acrylate, dicyclopentenyl (meth) acrylate, methyl (meth) acrylate, Propyl (meth) acrylate, butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, decyl (meta Aliphatic alkyl (meth) acrylates such as acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, glycerol (meth) acrylate, 2-hydroxyethyl (meth) acrylate , 3-chloro-2-hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate, allyl (meth) acrylate, 2-butoxyethyl (meth) acrylate, 2- (diethylamino) ethyl (meth) acrylate, 2- (dimethyl Amino) ethyl (meth) acrylate, γ- (meth) acryloxypropyltrimethoxysilane, 2-methoxyethyl (meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxydi Lopylene glycol (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, nonylphenoxypolypropylene glycol (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydipropylene glycolicol (meth) acrylate, phenoxypolypropylene glycol (meth) acrylate, Polybutadiene (meth) acrylate, polyethylene glycol-polypropylene glycol (meth) acrylate, polyethylene glycol-polybutylene glycol (meth) acrylate, polystyrylethyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopenta Nyl (meth) acrylate, dicyclopentenyl (meth) acryl , Isobornyl (meth) acrylate, methoxylated cyclodecatriene (meth) acrylate, phenyl (meth) acrylate; maleimide, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-butylmaleimide, N-hexyl Maleimide, N-octylmaleimide, N-dodecylmaleimide, N-stearylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide, 2-maleimidoethyl-ethylcarbonate, 2-maleimidoethyl-propylcarbonate, N-ethyl- (2- Maleimidoethyl) carbamate, N, N-hexamethylene bismaleimide, polypropylene glycol-bis (3-maleimidopropyl) ether, bis (2-maleimidoethyl) carbonate, 1,4-di And maleimides such as maleimide cyclohexane.

  Among these, since the hardness of the cured coating film is particularly excellent, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, pentaerythritol tetra A trifunctional or higher polyfunctional (meth) acrylate such as (meth) acrylate is preferred. These active energy ray-curable monomers (F) can be used alone or in combination of two or more.

  In the active energy ray-curable composition of the present invention, the use amount of the polymerizable fluorine surface-modified silica particles of the present invention can make the cured coating film of the composition sufficiently transparent, The total amount of energy beam curable resin (E) and active energy beam curable monomer (F) is preferably in the range of 0.01 to 10 parts by mass, and 0.05 to 5 parts by mass. More preferred is the range of parts. In addition, the polymerizable fluorine surface-modified silica particles of the present invention can exhibit sufficient water and oil repellency and antifouling properties with a small amount of use, but are used appropriately when it is desired to impart higher antifouling properties. The amount may be increased.

  The 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 irradiating ultraviolet rays as active energy rays to form a cured coating film, it is preferable to add a photopolymerization initiator (G) to the active energy ray curable composition to improve curability. Further, if necessary, a photosensitizer can be further added to improve curability. On the other hand, when ionizing radiation such as electron beam, α-ray, β-ray, and γ-ray is used, it cures quickly without using a photopolymerization initiator or photosensitizer. It is not necessary to add G) or a photosensitizer.

  Examples of the photopolymerization initiator (G) include intramolecular cleavage type photopolymerization initiators and hydrogen abstraction type photopolymerization initiators. Examples of the intramolecular cleavage type photopolymerization initiator include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy. 2-methylpropan-1-one, 4- (2-hydroxyethoxy) phenyl (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-2-morpholino (4-thiomethylphenyl) ) Acetophenone compounds such as propan-1-one and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone; benzoins such as benzoin, benzoin methyl ether and benzoin isopropyl ether; 2,4,6 -Trimethylbenzoindiphenylphosphine Kishido, 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 above photopolymerization initiators (G), excellent compatibility with the active energy ray curable resin (E) and the active energy ray curable monomer (F) in the active energy ray curable composition. Therefore, 1-hydroxycyclohexyl phenyl ketone and benzophenone are preferable, and 1-hydroxycyclohexyl phenyl ketone is particularly preferable. These photopolymerization initiators (G) can be used alone or in combination of two or more.

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

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

  Furthermore, the active energy ray-curable composition of the present invention is not limited to the effects of the present invention, depending on the purpose of use, characteristics, etc. Various compounding materials for the purpose of adjusting coating properties and coating film properties, such as various organic solvents, acrylic resins, phenol resins, polyester resins, polystyrene resins, urethane resins, urea resins, melamine resins, alkyd resins, epoxy resins, Various resins such as polyamide resin, polycarbonate resin, petroleum resin, fluororesin, various organic or inorganic particles such as PTFE (polytetrafluoroethylene), polyethylene, polypropylene, carbon, titanium oxide, alumina, copper, silica fine particles, polymerization start Agent, polymerization inhibitor, antistatic agent, antifoaming agent, viscosity modifier, light resistance stabilizer, weather resistance stabilizer, heat resistance Fixing agent, antioxidant, rust inhibitor, slip agent, wax, gloss adjuster, mold release agent, compatibilizer, conductivity modifier, pigment, dye, dispersant, dispersion stabilizer, silicone-based, hydrocarbon-based interface An activator or the like can be used in combination.

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

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

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

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

  The application method of the active energy ray-curable composition of the present invention varies depending on the application. For example, a gravure coater, roll coater, comma coater, knife coater, air knife coater, curtain coater, kiss coater, shower coater, wheeler coater, spin coater , Coating methods using dipping, screen printing, spraying, applicators, bar coaters, etc., or molding methods using various molds.

  Since the cured coating film of the active energy ray-curable composition of the present invention has excellent antifouling properties (ink repellency, fingerprint resistance, etc.), scratch resistance, etc., it can be applied and cured on the surface of an article. Further, antifouling property, scratch resistance and the like can be imparted to the surface of the article.

  Examples of articles that can be imparted with antifouling properties (ink repellency, fingerprint resistance, etc.) using the active energy ray-curable composition of the present invention include liquid crystal displays such as triacetyl cellulose (TAC) films (hereinafter “LCD”). Abbreviated as :) polarizing plate film; various display screens such as plasma display (PDP) and organic EL display; touch panel; housing or screen of electronic terminal such as mobile phone; color filter for liquid crystal display (hereinafter referred to as “CF”) A) transparent protective film; organic insulating film for liquid crystal TFT array; inkjet ink for forming electronic circuit; optical recording medium such as CD, DVD, Blu-ray disc; transfer film for insert mold (IMD, IMF); copy Rubber rollers for OA equipment such as copiers and printers; OA machines such as copiers and scanners Glass surface of the reading unit; Optical lenses such as cameras, video cameras, glasses; Windshields of watches such as watches; Glass surfaces; Windows for various vehicles such as automobiles and railway vehicles; Cover glasses or films for solar cells; Building materials; window glass for houses; woodworking materials such as furniture; artificial and synthetic leather; various plastic molded products such as housings for home appliances; and FRP bathtubs. By applying the active energy ray-curable composition of the present invention to these article surfaces and irradiating active energy rays such as ultraviolet rays to form a cured coating film, antifouling properties can be imparted to the article surfaces. . Moreover, it is also possible to add antifouling property to the article surface by adding the polymerizable fluorine surface-modified silica particles of the present invention to various paints suitable for each article, and applying and drying.

  Furthermore, examples of articles that can impart scratch resistance (scratch resistance) and antifouling properties using the active energy ray-curable composition of the present invention include prism sheets or diffusion sheets that are backlight members of LCDs. . Further, by adding the polymerizable fluorine surface-modified silica particles of the present invention to the prism sheet or the diffusion sheet coating material, it is possible to impart antifouling properties and scratch resistance (scratch resistance) to the coating film of the coating material. it can.

  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-described 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. This is preferable since

  In addition, when the 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, after the coating material is brought into contact with a mold having an uneven surface shape, It can also be applied to a transfer method in which an active energy ray is irradiated from the opposite side of the mold and cured, and the surface of the coat layer is embossed to impart antiglare properties.

  Hereinafter, the present invention will be described in more detail with reference to specific examples. The silica particles were observed by the following method.

[Observation of silica particles]
The particle shape was observed at a magnification of 100,000 using a field emission scanning electron microscope (FE-SEM) (“JSM6700” manufactured by JEOL Ltd.). Silica particles were dispersed in methyl isobutyl ketone, dropped onto a grid with a supporting film and observed after drying.

(Synthesis Example 1)
A glass flask equipped with a stirrer, a thermometer, a condenser, and a dropping device, 20 parts by mass of a perfluoropolyether compound having a hydroxyl group at both ends represented by the following formula (a2-1-1), and diisopropyl ether as a solvent 10 parts by mass, p-methoxyphenol 0.006 parts by mass as a polymerization inhibitor and 3.3 parts by mass of triethylamine as a neutralizing agent were added, stirring was started under an air stream, and methacrylic acid was maintained at 10 ° C. 3.1 parts by mass of acid chloride was added dropwise over 2 hours. After completion of the dropwise addition, the mixture was stirred at 10 ° C. for 1 hour, heated to 30 ° C. for 1 hour, then heated to 50 ° C. and stirred for 10 hours, and methacrylic acid was measured by gas chromatography. The disappearance of chloride was confirmed. Next, after adding 70 parts by mass of diisopropyl ether as a solvent, 80 parts by mass of ion-exchanged water was mixed, stirred, and allowed to stand, and washing by a method of separating and removing the aqueous layer was repeated three times. Subsequently, 0.02 parts by mass of p-methoxyphenol was added as a polymerization inhibitor, 8 parts by mass of magnesium sulfate was added as a dehydrating agent, and the mixture was allowed to stand for 1 day for complete dehydration, and then the dehydrating agent was filtered off. .

(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. (The average molecular weight is 1,500.)

  Subsequently, the solvent was distilled off under reduced pressure to obtain a compound having a poly (perfluoroalkylene ether) chain represented by the following formula (A-2-1) and methacryloyl groups at both ends thereof.

(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.)

Example 1
A glass flask equipped with a stirrer, a thermometer, a condenser, and a dropping device was charged with 70 g of methyl isobutyl ketone as a solvent and heated to 105 ° C. while stirring under a nitrogen stream. While maintaining the inside of the flask at 105 ° C., the poly (perfluoroalkylene ether) chain obtained in Synthesis Example 1 and 24 g of a compound having methacryloyl groups at both ends thereof, 46 g of 2-hydroxyethyl methacrylate, silica particles having a methacryloyl group (Nissan Chemical Industries, Ltd. “MIBK-SD-L”; average particle size 40 nm, solid content 31 mass% methyl isobutyl ketone dispersion) 96.8 g and methyl isobutyl ketone 30 g mixed with a radical polymerization initiator Three types of dripping solutions with a polymerization initiator solution in which 10.5 g of t-butylperoxy-2-ethylhexanoate was dissolved in 43.2 g of methyl isobutyl ketone were set in separate dripping apparatuses, and the inside of the flask was 105 ° C. The solution was added dropwise in 2 hours at the same time. After completion of dropping, the mixture was stirred at 105 ° C. for 5 hours, 0.0604 g of p-methoxyphenol and 0.4532 g of 3,5-dibutyl-4-hydroxytoluene as a polymerization inhibitor, and 0.0453 g of tin octylate as a urethanization catalyst. And stirring was started under an air stream, and 50 g of 2-acryloyloxyethyl isocyanate was added dropwise over 1 hour while maintaining 60 ° C. After completion of the dropwise addition, the mixture was stirred at 60 ° C. for 1 hour, then heated to 80 ° C. and stirred for 4 hours. As a result, IR spectrum measurement confirmed the disappearance of the absorption peak due to the isocyanate group. The obtained reaction solution was purified by filtration using a polytetrafluoroethylene (PTFE) filter having a pore size of 0.2 μm, and then methyl isobutyl ketone was added to the filtrate to obtain polymerizable fluorine surface-modified silica particles (1). A methyl isobutyl ketone dispersion containing 30% by mass was obtained.

  An electron micrograph (100,000 times) of the polymerizable fluorine surface-modified silica particles (1) obtained above is shown in FIG. 1, and an electron micrograph (100,000 times) of silica particles having a methacryloyl group used as a raw material. It is shown in 2. From these photographs, in the polymerizable fluorine surface-modified silica particles (1) in FIG. 1, the silica particle surface is covered with a fluororesin, whereas in the silica particles having a methacryloyl group used as a raw material in FIG. It was found that no such resin was present on the silica particle surface. In addition, the part which particle | grains have adhered in the photograph of FIG. 1 and 2 is a grid with a support film.

(Comparative Example 1)
A glass flask equipped with a stirrer, a thermometer, a condenser, and a dropping device was charged with 700 g of methyl isobutyl ketone as a solvent and heated to 105 ° C. while stirring under a nitrogen stream. While maintaining the inside of the flask at 105 ° C., the poly (perfluoroalkylene ether) chain obtained in Synthesis Example 1 and 240 g of a compound having a methacryloyl group at both ends, 460 g of 2-hydroxyethyl methacrylate, and 851 g of methyl isobutyl ketone were mixed. Three different dropping solutions of the solution and a polymerization initiator solution obtained by dissolving 105.1 g of t-butylperoxy-2-ethylhexanoate as a radical polymerization initiator in 550.5 g of methyl isobutyl ketone were respectively added to separate dropping devices. The flask was added dropwise at the same time in 2 hours while keeping the inside of the flask at 105 ° C. After completion of dropping, the mixture was stirred at 105 ° C. for 5 hours, 0.484 g of p-methoxyphenol and 3.631 g of 3,5-dibutyl-4-hydroxytoluene as a polymerization inhibitor, and 0.3784 g of tin octylate as a urethanization catalyst. And stirring was started under an air stream, and 50 g of 2-acryloyloxyethyl isocyanate was added dropwise over 1 hour while maintaining 60 ° C. After completion of the dropwise addition, the mixture was stirred at 60 ° C. for 1 hour, then heated to 80 ° C. and stirred for 4 hours. As a result, the disappearance of the absorption peak of the isocyanate group was confirmed by IR spectrum measurement. The obtained reaction solution was purified by filtration using a polytetrafluoroethylene (PTFE) filter having a pore size of 0.2 μm, and then methyl isobutyl ketone was added to the filtrate to obtain polymerizable fluorine surface-modified silica particles (1). A methyl isobutyl ketone solution containing 30% by mass was obtained.

  An active energy ray-curable composition was prepared according to the following using the polymerizable fluorine surface-modified silica particles (1) and the fluorine-containing curable resin (1) obtained above.

(Example 2)
4.995 g of ultraviolet curable urethane acrylate resin (“Unidic 17-806” manufactured by DIC Corporation; butyl acetate solution with a resin content of 80% by mass), polymerizable fluorine surface-modified silica particles (1) obtained in Example 1 A dispersion of 0.0133 g (0.004 g as the silica particles), 0.2 g of photopolymerization initiator (“Irgacure 184” manufactured by BASF Japan Ltd .; 1-hydroxycyclohexyl phenyl ketone) and 4.992 g of methyl ethyl ketone are mixed and stirred. Thus, an active energy ray-curable composition containing 0.1% by mass in the solid content as the addition amount of the polymerizable fluorine surface-modified silica particles (1) was obtained.

(Comparative Example 2)
0.0133 g of a dispersion of polymerizable fluorine surface-modified silica particles (1) used in Example 2 was added to 0.0133 g of the fluorine-containing curable resin (1) obtained in Comparative Example 1 (0.004 g as the resin). The active energy ray-curable composition containing 0.1% by mass in the solid content as the addition amount of the polymerizable fluorine surface-modified silica particles (1) was obtained in the same manner as in Example 3 except that the above was changed.

(Comparative Example 3)
A dispersion of 0.0133 g of the polymerizable fluorine surface-modified silica particles (1) used in Example 2 was added to 0.0107 g of the fluorine-containing curable resin (1) obtained in Comparative Example 1 (0.0032 g as the resin). ) And silica particles having a methacryloyl group (“MIBK-SD-L” manufactured by Nissan Chemical Industries, Ltd .; average particle size 40 nm, solid content 31 mass% methyl isobutyl ketone dispersion) 0.0026 g (0.0008 g as the silica particles) ), Except that the methyl ethyl ketone was changed to 4.992 g, the same as in Example 2, 0.1% by mass in the solid content as the total addition amount of the fluorine-containing curable resin (1) and silica particles having a methacryloyl group An active energy ray-curable composition was obtained.

(Comparative Example 4)
UV curable urethane acrylate resin (“Unidic 17-806” manufactured by DIC Corporation; butyl acetate solution having a resin content of 80% by mass), photopolymerization initiator (“Irgacure 184” manufactured by BASF Japan Ltd.); 1-hydroxycyclohexyl 0.2 g of phenylketone) and 5 g of methyl ethyl ketone were mixed and stirred to obtain an active energy ray-curable composition containing no additive.

  Using the active energy ray-curable composition obtained in Example 2 and Comparative Examples 2 to 4 above, water and n-dodecane were prepared as follows to prepare a coating film and evaluate the antifouling property. The contact angle was measured and the antifouling property was evaluated.

[Production of coated film]
An 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 coated film was cured by irradiating with ultraviolet rays (UV) with an ultraviolet curing device (under a nitrogen atmosphere, a high-pressure mercury lamp, an ultraviolet irradiation amount of ² kJ / m ² ) to produce a coated film.

[Measurement of contact angle of water and n-dodecane]
About the cured coating film surface of the active energy ray curable composition of the coating film obtained above, water and n-dodecane were used using a contact angle measuring device (“MODEL CA-W150” manufactured by Kyowa Interface Science Co., Ltd.). The contact angle of was measured.

[Evaluation of dirt adhesion prevention]
On the coated surface of the coated film, a line is drawn with an oil-based felt pen (Magic Ink Large Black, manufactured by Teranishi Chemical Industry Co., Ltd.), and the adhesion of the black ink is visually observed to evaluate the antifouling property. It was. The evaluation criteria are as follows.
○: Ink repelling occurs and the line width is less than 50% of the width of the tip of the felt pen.
Δ: Ink repelling occurs and the line width is 50% or more and less than 100% of the width of the tip of the felt pen.
X: The ink can be drawn cleanly on the surface without repelling at all.

  The measurement and evaluation results are shown in Table 1.

  From the result of Example 2, it is a cured coating film of an active energy ray-curable composition containing the polymerizable fluorine surface-modified silica particles (1) of the present invention in an extremely small amount of 0.1% by mass in the solid content. In addition, the contact angles of water and n-dodecane were as high as 94 ° and 44 °, respectively, and it was found that the antifouling property was extremely excellent.

  On the other hand, from the result of Comparative Example 2, the cured coating film of the active energy ray-curable composition containing 0.1% by mass of the fluorine-containing curable resin (1) produced in Comparative Example 1 in the solid content is water and It was found that the contact angles of n-dodecane were 80 ° and 39 °, respectively, lower than Example 2 using the polymerizable fluorine surface-modified silica particles (1) of the present invention and inferior in soil adhesion prevention.

  From the results of Comparative Example 3, the total amount of the fluorine-containing curable resin (1) produced in Comparative Example 1 and the silica particles having a methacryloyl group used as a raw material for producing the polymerizable fluorine surface-modified silica particles of the present invention. As the cured coating film of the active energy ray-curable composition containing 0.1% by mass in the solid content, the contact angles of water and n-dodecane are 78 ° and 38 °, respectively, and the polymerizable fluorine surface-modified silica of the present invention It was found to be lower than Example 2 using the particles (1) and inferior in adhesion to dirt.

  In Comparative Example 4 in which no additive was added, the contact angles of water and n-dodecane were very low at 53 ° and 17 °, respectively, and it was found that the adhesion of dirt could not be prevented.

Claims (4)

  From the group consisting of a poly (perfluoroalkylene ether) chain and a compound (A) having a polymerizable unsaturated group at both ends thereof, a hydroxyl group, an isocyanate group, an epoxy group, a carboxyl group, an acid anhydride group and a carboxylic acid halide group Surface-modified silica particles obtained by polymerizing a polymerizable unsaturated monomer (B) having at least one selected functional group (b) and silica particles (C) having a polymerizable unsaturated group as essential components (P) has at least one selected from the group consisting of a hydroxyl group, an isocyanate group, an epoxy group, a carboxyl group, an acid anhydride group, and a carboxylic acid halide group, which is reactive to the functional group (b). Polymeric fluorine surface-modified silica particles obtained by reacting a compound (D) having a functional group (d) and a polymerizable unsaturated group.   An active energy ray-curable composition comprising the polymerizable fluorine surface-modified silica particles according to claim 1 and an active energy ray-curable resin (E) or an active energy ray-curable monomer (F). object.   A cured product obtained by applying the active energy ray-curable composition according to claim 2 to a substrate and irradiating and curing the active energy ray.   An article having a cured coating film of the active energy ray-curable composition according to claim 2.