JP5584989B2 - Surface-modified silica particles and active energy ray-curable resin composition using the same - Google Patents

Description

  The present invention relates to a surface-modified silica particle capable of imparting antifouling properties to a coating film and an active energy ray-curable resin composition containing the silica particle.

  In recent years, liquid crystal displays, plasma displays, organic EL displays, etc., which are flat panel displays (FPD), are applied as information display devices to home TVs, mobile phones, car navigation systems for automobiles, operation panels for various devices, and the like. . 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.

  Here, the coating agent containing silica particles is used for the purpose of imparting anti-glare properties (AG; anti-glare) by applying it to a film on the outermost surface of a liquid crystal display or a plasma display (for example, patent document). 1). In addition, it is known that the coating agent containing silica particles has an effect of preventing adhesion of dirt such as fingerprints and making the dirt inconspicuous because the coated surface is uneven.

  However, since silica particles are an inorganic compound, there is a problem of poor affinity with binder resins and organic solvents. As a method for solving this problem, it has been proposed to improve the dispersibility in a binder resin or an organic solvent by modifying the surface of silica particles with a silicone compound such as polydimethylsiloxane (see, for example, Patent Document 2). ). However, sufficient antifouling properties were not obtained with silica particles modified only with a silicone compound.

  On the other hand, by using reactive silica particles in which the surface of the silica particles is modified with a polymerizable unsaturated group as a coating material in which the binder resin is an active energy ray curable resin, the scratch resistance of the coating film surface made of the coating material is improved. Improvement has been proposed (see, for example, Patent Document 3). However, the coating material using the reactive silica particles has a problem that although the scratch resistance is improved, a sufficient effect cannot be obtained with respect to the antifouling property.

JP-A-7-181306 JP-A-3-258866 Japanese Patent Laid-Open No. 9-100111

  The problem to be solved by the present invention is to provide surface-modified silica particles capable of imparting high antifouling properties and an active energy ray-curable resin composition containing the silica particles.

  As a result of diligent research, the inventors have made antifouling properties by modifying the surface of the silica particles with a silicone compound such as a polyalkylsiloxane chain and an active energy ray polymerizable group such as a (meth) acryloyl group. The present invention has been completed by finding that an excellent coating material can be obtained.

That is, the present invention is, on the surface of the silica particles via a silyloxy group, a polyalkyl siloxane chain or polyaryl siloxane chain, and the front surface-modified silica particles obtained by modifying the active energy ray-polymerizable group, the polymerizable unsaturated monomer A polymer structure (α) of a monomer and a poly (perfluoroalkylene ether) chain (β), and a plurality of the polymer structures (α) are interposed via the poly (perfluoroalkylene ether) chain (β). And a fluorine-containing polymerizable resin having a resin structure having an active energy ray-polymerizable group in the side chain of the polymer structure (α). A resin composition is provided.

  The surface-modified silica particles of the present invention can be used as an additive for various coating materials, and can impart excellent antifouling properties to articles coated with the coating materials. Therefore, the active energy ray-curable resin composition containing the surface-modified silica particles of the present invention is an antireflection material used in FPDs such as protective films, liquid crystal displays, plasma displays, and organic EL displays that require antifouling properties. Useful for films and antiglare films. In particular, by applying the active energy ray-curable resin composition containing the surface-modified silica particles of the present invention to the outermost surface of the touch panel, it is possible to eliminate the difficulty in viewing the screen caused by dirt such as fingerprints. Useful.

  More specifically, a coating material for a protective film for a polarizing plate of a liquid crystal display typified by a triacetyl cellulose (TAC) film, a housing for various home appliances, a housing for a mobile phone, a hard coat for a liquid crystal display for a mobile phone, etc. It can be used for a wide range of materials. It is also useful for metal-plated articles or glass windows where dirt such as fingerprints is conspicuous.

  As silica particles used in the present invention, powder silica and colloidal silica can be used. The average particle diameter of the silica particles is preferably 10 to 1,000 nm, but 10 to 500 is preferable and 10 to 100 is more preferable when obtaining a more transparent active energy ray-curable resin composition. The silica particles used in the present invention may be spherical, hollow, porous, rod-like, plate-like, fibrous, or indefinite, but spherical ones are preferred. In the present invention, the average particle diameter of the silica particles is a value measured with a transmission electron microscope.

  In the present invention, it is preferable to use colloidal silica in which fine silica particles are dispersed in water or an organic solvent as silica particles. When using this colloidal silica, it is preferable to use the dispersion liquid as it is. As the colloidal silica dispersion, the medium is preferably an organic solvent. Examples of the organic solvent include methanol, isopropyl alcohol, ethylene glycol, butanol, ethylene glycol monopropyl ether, methyl ethyl ketone, methyl isobutyl ketone, toluene, xylene, dimethylformamide and the like. Further, a mixed solvent in which two or more of these are used in combination or a mixed solvent in which a water-soluble organic solvent and water are used in combination may be used. Among these organic solvents, methanol, isopropyl alcohol, methyl ethyl ketone, and xylene are preferable because they can be easily modified on the silica surface described later.

  In the present invention, the method of modifying the silica particle surface with a polyalkylsiloxane chain or polyarylsiloxane chain is the use of an alkoxysilane (A) having a polyalkylsiloxane chain or polyarylsiloxane chain to remove the silica particle surface from silanol. A method using an alcohol reaction, or an alkoxysilane (A) having a polyalkylsiloxane chain or a polyarylsiloxane chain is hydrolyzed in the presence of water to generate a silanol group, and then the silanol group and the silanol group on the silica surface And a method of dehydrating condensation between an alcohol having a polyalkylsiloxane chain or a polyarylsiloxane chain and a silanol group on the silica surface.

  Further, as another method for modifying the silica particle surface with a polyalkylsiloxane chain or a polyarylsiloxane chain, an alkoxysilane having a reactive group (generally referred to as a silane coupling agent; hereinafter referred to as “compound (a1)” And the functional group capable of reacting with the reactive group to form a chemical bond, and a polyalkylsiloxane chain or polyarylsiloxane. And a method of reacting a compound (a2) having a chain with a functional group capable of reacting with a reactive group of the compound (a1) and the compound (a1) to form a chemical bond and a polyalkylsiloxane chain. Alternatively, a compound (a2) having a polyarylsiloxane chain is reacted in advance to form a polyalkylsiloxane chain or a polyarylsiloxane chain. To obtain the compound having the Le siloxane chain and alkoxysilane, the method reacting the compound with the silica particles it may also be mentioned.

  As a reactive group which the said compound (a1) has, an epoxy group, an amino group, a mercapto group, an isocyanate group etc. are mentioned, for example. Specific examples of the compound (a1) include 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3- Compounds having an epoxy group such as glycidoxypropyltriethoxysilane; N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N Compounds having an amino group such as 2- (aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane; 3-mercaptopropylmethyldimethoxysilane, 3-mercapto Mercapto groups such as propyltrimethoxysilane Compounds having; and compounds having a 3-isocyanate propyltriethoxysilane isocyanate groups, and the like.

  The functional group that the compound (a2) has is selected depending on the reactive group that the compound (a1) has. When the reactive group that the compound (a1) has is an epoxy group, the functional group that the compound (a2) has is preferably a carboxyl group. Moreover, when the reactive group which a compound (a1) has is an amino group, the functional group which the said compound (a2) has is preferably an epoxy group. Furthermore, when the reactive group that the compound (a1) has is a mercapto group, the functional group that the compound (a2) has is preferably an isocyanate group, and when the reactive group that the compound (a1) has is an isocyanate group, The functional group that the compound (a2) has is preferably a hydroxyl group or a mercapto group. The compound (a2) preferably has a functional group at one end of a polyalkylsiloxane chain or a polyarylsiloxane chain.

  Among the above combinations, the case where the reactive group of the compound (a1) is an isocyanate group and the functional group of the compound (a2) is a hydroxyl group is preferable because the reaction is easy.

  Examples of the compound that forms the polyalkylsiloxane chain or polyarylsiloxane chain of the compound (a2) include polydimethylsiloxane and polydiphenylsiloxane. In addition, the organic groups bonded to the silicon atom of these polysiloxanes may be all the same or different.

  When the compound that forms the polyalkylsiloxane chain is polydimethylsiloxane, the molecular weight of the polydimethylsiloxane is preferably 1,000 to 10,000, and more preferably 2,500 to 6,000. When the molecular weight of polydimethylsiloxane is within this range, the antifouling property is further improved.

  As a method for modifying the surface of silica particles with an active energy ray polymerizable group in the present invention, an alkoxysilane (B) having an active energy ray polymerizable group is used, and a dealcoholization reaction with silanol on the surface of silica particles is used. And using the alkoxysilane (B) having an active energy ray-polymerizable group, the alkoxysilane (B) is hydrolyzed in the presence of water to generate a silanol group, and then the silanol group and the silica surface And a method of dehydrating and condensing with a silanol group. Examples of the active energy ray polymerizable group include a vinyl group, a (meth) acryl group, a vinyl ether group, an epoxy group, and an oxetanyl group. In the present invention, “(meth) acryl” refers to one or both of methacryl and acryl, “(meth) acryloyl” refers to one or both of methacryloyl and acryloyl, and “(meth) acrylate” Means one or both of methacrylate and acrylate.

  Specific examples of the alkoxysilane (B) include compounds having a vinyl group such as vinyltrimethoxysilane, vinyltriethoxysilane, and p-styryltrimethoxysilane; 3-methacryloxypropylmethyldimethoxysilane, 3-methacrylic Compounds having a methacryloyl group such as loxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane; compounds having an acryloyl group such as 3-acryloxypropyltrimethoxysilane; 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, etc. Compounds having an epoxy group; 3 - such as - [(.gamma. triethoxysilyl) propylonitrile carboxymethyl] -3- compound having an oxetanyl group such ethyloxetane and the like.

  As another method for modifying the surface of the silica particle with an active energy ray polymerizable group, an alkoxysilane having a reactive group (hereinafter referred to as “compound (b1)”) is applied to the surface of the silica particle in the same manner as described above. A method of reacting a compound (b2) having a functional group capable of reacting with the reactive group to form a chemical bond and an active energy ray polymerizable group after the dehydration or dealcohol condensation reaction, and The compound (a2) having a functional group capable of reacting with the reactive group of the compound (b1) and the compound (b1) to form a chemical bond and an active energy ray polymerizable group is reacted in advance to produce an active energy ray. A method of reacting this compound with silica particles after obtaining a compound having a polymerizable group and alkoxysilane is also mentioned.

  As the compound (b1), the same compound as the compound (a1) can be used. Moreover, the functional group which the said compound (b2) has is selected by the reactive group which the compound (b1) has. When the reactive group that the compound (b1) has is an epoxy group, the functional group that the compound (b2) has is preferably a carboxyl group. Moreover, when the reactive group which a compound (b1) has is an amino group, the functional group which the said compound (b2) has is preferably an epoxy group. Furthermore, when the reactive group that the compound (b1) has is a mercapto group, the functional group that the compound (b2) has is preferably an isocyanate group, and when the reactive group that the compound (b1) has is an isocyanate group, The functional group of the compound (b2) is preferably a hydroxyl group or a mercapto group.

  Among the above combinations, the case where the reactive group of the compound (b1) is an isocyanate group and the functional group of the compound (b2) is a hydroxyl group is preferable because the reaction is easy.

  Specific examples of the compound (b2) include, for example, 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) acryloloxyethyl-2-hydroxyethyl phthalate, terminal hydroxyl group-containing lactone modification (meta Compounds having a hydroxyl group such as acrylate; compounds having an isocyanate group such as 2- (meth) acryloyloxyethyl isocyanate and 2- (2- (meth) acryloyloxyethoxy) ethyl isocyanate; glycidyl methacrylate, 4-hydroxybutyl acrylate glycidyl ether Compounds having an epoxy group such as: (meth) acrylic acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl phthalic acid, compounds having a carboxyl group such as itaconic acid, and the like.

  When the reactive group that the compound (a1) or the compound (b1) has is an isocyanate group and the functional group that the compound (a2) or the compound (b2) has is a hydroxyl group, the compound (a1) or the compound (b1) ) Is preferably 0.5 to 1.1 based on 1 mole of the compound (a2) or the compound (b2), and does not leave the unreacted compound (a1) or the compound (b1). It is especially preferable to set it as 0.9-1.0 mol by a point.

  In the above case, the reaction between the compound (a1) and the compound (a2) or the reaction between the compound (b1) and the compound (b2) can be performed without using a solvent or with a solvent. The use of a solvent is preferable in that the fluidity of the reaction solution is improved. Examples of the solvent include ester solvents such as ethyl acetate, butyl acetate, and propylene glycol monomethyl ether acetate; ether solvents such as diisopropyl ether, dimethoxyethane, and diethylene glycol dimethyl ether; halogen solvents such as dichloromethane and dichloroethane; toluene, xylene, and the like. Aromatic solvents such as: methyl ketones such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; and aprotic polar solvents such as dimethylformamide and dimethyl sulfoxide. Among these, ester solvents; ketone solvents; ether solvents are preferable.

  In order to promote the reaction between the compound (a1) and the compound (a2) or the reaction between the compound (b1) and the compound (b2), the reaction is preferably performed in the presence of a urethanization catalyst. Examples of the urethanization catalyst include amines such as pyridine, pyrrole, triethylamine, diethylamine and dibutylamine; phosphines such as triphenylphosphine and triethylphosphine; dibutyltin dilaurate, octyltin trilaurate, octyltin diacetate, dibutyltin diacetate Organic tin compounds such as acetate and tin octylate; organometallic compounds such as zinc octylate and the like. Moreover, it is preferable to use an organic tin compound and amines together because the urethanization reaction proceeds smoothly.

  The surface modification amount of the polyalkylsiloxane chain or polyarylsiloxane chain with respect to the mass of the silica particles is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the silica particles, from the viewpoint of efficiently modifying the coating film surface. 0.1-5 mass parts is preferable. Moreover, the usage-amount of the compounds (b1) and (b2) used for the surface modification with respect to the mass of a silica particle is 10-200 mass parts by the total amount of a compound (b1) and (b2) with respect to 100 mass parts of silica particles. Is preferable, and 10-50 mass parts is more preferable.

  The active energy ray-curable resin composition of the present invention is an active energy ray-curable resin composition containing the surface-modified silica particles. The compounding amount of the surface-modified silica particles is 0.5 to 30 mass with respect to 100 mass parts of the nonvolatile content in the active energy ray-curable resin composition (excluding the polymerization initiator and the fluorine-containing polymerizable resin described later). Part. In particular, the resin composition to be added is preferably 2 to 20 parts by mass, since it does not impair the physical properties such as the original coating film hardness and can efficiently modify the coating film surface. Is more preferable.

  The active energy ray-curable resin composition of the present invention comprises a polymer structure (α) of a polymerizable unsaturated monomer and a poly (perfluoroalkylene ether) chain (β) in addition to the surface-modified silica particles. And a plurality of the polymer structures (α) are knotted via the poly (perfluoroalkylene ether) chain (β), and active energy rays are formed on the side chain of the polymer structure (α). When the fluorine-containing polymerizable resin (C) having a resin structure having a polymerizable group is contained, the antifouling property is further improved, which is preferable.

  The fluorine-containing polymerizable resin (C) has a polymer structure (α) of a polymerizable unsaturated monomer and a poly (perfluoroalkylene ether) chain (β), and a plurality of the polymer structures (α ) Are knotted through the poly (perfluoroalkylene ether) chain (β) and have a resin structure having an active energy ray polymerizable group in the side chain of the polymer structure (α). .

  Examples of the polymerizable unsaturated monomer constituting the polymer structure (α) include acrylic monomers, aromatic vinyl monomers, vinyl ester monomers, maleimide monomers, and the like. The polymer structure (α) is a structural part of a linear structure that is a homopolymer or a copolymer thereof. In order to introduce an active energy ray polymerizable group into the side chain of the polymer structure (α), a polymerizable unsaturated monomer (c2) having a reactive group in part or all of the monomer component is used. . Therefore, the polymer structure (α) is a homopolymer structure of the polymerizable unsaturated monomer (c2), or the polymerizable unsaturated monomer (c2) and other polymerizable unsaturated monomers. It becomes a copolymer structure with the monomer. In the present invention, as described later, when the polymerizable unsaturated monomer is polymerized to form a polymer structure (α), a poly (perfluoroalkylene ether) chain and both ends thereof are polymerizable unsaturated. It is preferable to copolymerize the compound (c1) having a structural moiety having a group together with the polymerizable unsaturated monomer. In this case, the polymer structure (α) includes a structural moiety derived from the compound (c1). It is.

  Here, examples of the reactive group present in the polymerizable unsaturated monomer (c2) include a hydroxyl group, an isocyanate group, a glycidyl group, and a carboxyl group, and the polymerizable unsaturated monomer (c2). ) 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-phenoxy Hydroxyl group-containing unsaturated monomers such as propyl (meth) acrylate, 2- (meth) acryloyloxyethyl-2-hydroxyethyl phthalate, terminal hydroxyl group-containing lactone-modified (meth) acrylate; 2- (meth) acryloyloxyethyl Isocyanate group-containing unsaturated monomers such as isocyanate and 2- (2- (meth) acryloyloxyethoxy) ethyl isocyanate; Glycidyl group-containing unsaturated monomers such as glycidyl methacrylate and 4-hydroxybutyl acrylate glycidyl ether; ) Carboxyl group-containing unsaturated monomers such as acrylic acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl phthalic acid and itaconic acid.

  Other polymerizable unsaturated monomers that can be copolymerized with the polymerizable unsaturated monomer (c2) include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n- Butyl (meth) acrylate, isobutyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, n-heptyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) Alkyl (meth) acrylates such as acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate; styrene, α-methylstyrene, p-methyl Styrene, p-methoxystyrene Aromatic vinyls such emissions; maleimide, methyl maleimide, ethyl maleimide, propyl maleimide, butyl maleimide, hexyl maleimide, octyl maleimide, dodecyl maleimide, stearyl maleimide, phenyl maleimide, maleimide such as cyclohexyl maleimide.

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

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

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

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

  In addition, the poly (perfluoroalkylene ether) chain (β) is a poly (perfluoroalkylene ether) from the viewpoint of excellent dirt wiping and slipperiness and easy improvement in solubility in non-fluorinated curable resin compositions. ) The total number of fluorine atoms contained in one chain is preferably in the range of 18 to 200, particularly preferably in the range of 25 to 80.

  Here, in order to bond both ends of the poly (perfluoroalkylene ether) chain (β) to the polymer structure (α) of the polymerizable unsaturated monomer, the polymerizable unsaturated monomer having a reactive group A compound (c1) having a structural site having a poly (perfluoroalkylene ether) chain and polymerizable unsaturated groups at both ends thereof, together with a polymerizable unsaturated monomer having (c2) as an essential monomer component A polymer structure (α) is formed by copolymerizing or polymerizing a polymerizable unsaturated monomer having a polymerizable unsaturated monomer (c2) having a reactive group as an essential monomer component. Then, the compound (c1) having a functional group capable of forming a chemical bond by reacting with a reactive group of the polymerizable unsaturated monomer (c2) at both ends of the poly (perfluoroalkylene ether) chain. ').

  Next, the active energy ray polymerizable group present in the side chain of the polymer structure (α) is a vinyl group, (meth) acryl group, vinyl ether group, epoxy group, which exhibits curability when irradiated with active energy rays, An oxetanyl group etc. are mentioned. Here, it is preferable to select the active energy ray polymerizable group present in the side chain of the polymer structure (α) in accordance with the type of the active energy ray polymerizable group of the surface-modified silica. For example, when the active energy ray polymerizable group of the surface-modified silica is a radical polymerizable group such as a (meth) acryl group, the active energy ray polymerizable group present in the side chain of the polymer structure (α). When the radically polymerizable group such as a (meth) acryl group is used and the active energy ray polymerizable group of the surface-modified silica is a cationic polymerizable group such as a vinyl ether group, an epoxy group, or an oxetanyl group, the polymer structure The active energy ray polymerizable group present in the side chain of (α) is also preferably a cationic polymerizable group such as a vinyl ether group, an epoxy group, or an oxetanyl group. Among these, specific examples in the case where the active energy ray polymerizable group present in the side chain of the polymer structure (α) is a radical polymerizable group are represented by the following structural formulas U-1 to U-3. Things.

  In order to introduce the active energy ray polymerizable group into the side chain of the polymer structure (α), after forming the polymer structure (α), the reaction existing in the side chain of the polymer structure (α) A method in which the functional group reacts with the compound (c3) having a functional group capable of reacting with the reactive group to form a chemical bond and an active energy ray polymerizable group is mentioned.

  Therefore, the fluorine-containing polymerizable resin (C) specifically includes a compound (c1) having a poly (perfluoroalkylene ether) chain and a structural portion having a polymerizable unsaturated group at both ends thereof, and reactivity. A reactive group possessed by the polymerizable unsaturated monomer (c2) in a polymer (P1) obtained by copolymerizing a polymerizable unsaturated monomer having a group (c2) as an essential monomer component Obtained by reacting a compound (c3) containing a functional group capable of forming a chemical bond by reaction with an active energy ray polymerizable group (hereinafter referred to as “fluorinated polymerizable resin (C-1)”) .), Or the polymer (P2) of the polymerizable unsaturated monomer (c2) having a reactive group is reacted with the poly (perfluoroalkylene ether) chain and the polymer (P2) at both ends thereof. Reacts with sex groups to form chemical bonds A compound (c3) having a functional group capable of reacting with the reactive group of the polymer (P2) and a functional group capable of forming a chemical bond and an active energy ray polymerizable group It is preferable that it is obtained by reacting with (hereinafter referred to as “fluorinated polymerizable resin (C-2)”) because its industrial production is easy.

  Here, the compound (c1) having a structural part having a poly (perfluoroalkylene ether) chain and a polymerizable unsaturated group at both ends used for producing the fluorine-containing polymerizable resin (c1) is as described above. What has the polymerizable unsaturated group shown by the following structural formula U'-1-U'-4 at the both terminal of the poly (perfluoroalkylene ether) chain | strand ((beta)) is mentioned, for example.

  Among the above-mentioned polymerizable unsaturated groups, the structural formula U′-1 is particularly preferable because the compound (c1) itself is easily available and manufactured, or has excellent reactivity with the polymerizable unsaturated monomer. The acryloyloxy group represented or the methacryloyloxy group represented by Structural Formula U′-2 is preferable.

  Among the compounds (c1), examples of the compound having the acryloyloxy group or methacryloyloxy group include those represented by the following structural formulas c1-1 to c1-10. In the following structural formulas, “—PFPE—” represents a poly (perfluoroalkylene ether) chain.

  Among the above-mentioned compounds (c1), they are particularly represented by the structural formulas c1-1 and c1-5 from the viewpoint of easy industrial production and easy polymerization reaction when producing the polymer (P1). Those are preferred.

  In order to produce the compound (c1), for example, a method obtained by dehydrochlorinating (meth) acrylic acid chloride to a perfluoropolyether having one hydroxyl group at both ends, (meth) acrylic acid A method obtained by dehydration reaction, a method obtained by urethanation of 2- (meth) acryloyloxyethyl isocyanate, a method obtained by esterification of itaconic anhydride, perfluoro having one carboxyl group at both ends For a polyether, a method obtained by esterifying 4-hydroxybutyl acrylate glycidyl ether, a method obtained by esterifying glycidyl methacrylate, and a perfluoropolyether having one isocyanate group at both ends. , 2-hydroxyethylacrylamide reaction method And the like. Among these, a method obtained by dehydrochlorinating (meth) acrylic acid chloride to perfluoropolyether having one hydroxyl group at both ends, and urethanization reaction of 2- (meth) acryloyloxyethyl isocyanate The method obtained by this is particularly preferable in that it is easily obtained synthetically.

  Here, the method for producing the polymer (P1) includes the compound (c1), a polymerizable unsaturated monomer having a reactive group (c2), and, if necessary, other polymerizable unsaturated monomers. Can be polymerized using a polymerization initiator in an organic solvent. As the organic solvent used here, ketones, esters, amides, sulfoxides, ethers, hydrocarbons are preferable. Specifically, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, butyl acetate, Examples include propylene glycol monomethyl ether acetate, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, toluene, xylene and the like. These are appropriately selected in consideration of boiling point, compatibility, and polymerizability. Examples of the polymerization initiator include peroxides such as benzoyl peroxide and azo compounds such as azobisisobutyronitrile. Furthermore, chain transfer agents such as lauryl mercaptan, 2-mercaptoethanol, thioglycerol, ethylthioglycolic acid, octylthioglycolic acid and the like can be used as necessary.

  The molecular weight of the obtained polymer (P1) needs to be in a range where crosslinking insolubilization does not occur during polymerization, and crosslinking insolubilization may occur if the molecular weight is too high. Within that range, the polymer (P1) has a number average molecular weight of 800 to 800 in that the number of polymerizable unsaturated groups in one molecule of the finally obtained fluorine-containing polymerizable resin (C-1) increases. It is preferably in the range of 3,000, particularly 1,000 to 2,000, and the weight average molecular weight is preferably in the range of 1,500 to 20,000, particularly 2,000 to 5,000.

  The polymer (P1) thus obtained reacts with the reactive group of the polymer (P1) (reactive group of the polymerizable unsaturated monomer (c2)) to form a chemical bond. The target fluorine-containing polymerizable resin (C-1) is obtained by reacting the compound (c3) containing a functional group that can be formed and a polymerizable unsaturated group.

  Here, as for the functional group which the said compound (c3) has, a hydroxyl group, an isocyanate group, a glycidyl group, a carboxyl group etc. are mentioned, for example. For example, when the reactive group which the polymer (P1) has is a hydroxyl group, an isocyanate group is mentioned as a functional group which the compound (c3) has, and the reactive group which the polymer (P1) has is an isocyanate group. In this case, the functional group of the compound (c3) includes a hydroxyl group. When the reactive group of the polymer (P1) is a glycidyl group, the functional group of the compound (c3) includes a carboxyl group. When the reactive group possessed by the polymer (P1) is a carboxyl group, a glycidyl group can be mentioned as a functional group possessed by the compound (c3).

  Specific examples of such compound (c3) include those exemplified as the polymerizable unsaturated monomer (c2) having a reactive group, 2-hydroxy-3-acryloyloxypropyl methacrylate, penta Examples include erythritol triacrylate and dipentaerythritol pentaacrylate.

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

  A method of reacting the polymer (P1) with a compound (c3) containing a functional group capable of forming a chemical bond by reacting with a reactive group of the polymer (P1) and a polymerizable unsaturated group, What is necessary is just to carry out on the conditions which the polymerizable unsaturated group in a compound (c3) does not superpose | polymerize, for example, it is preferable to make it react by adjusting temperature conditions in the range of 30-120 degreeC. 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 reactive group of the polymer (P1) is a hydroxyl group and the functional group of the compound (c3) is an isocyanate group, or the reactive group of the polymer (P1) is an isocyanate group. When the functional group of the compound (c3) is a hydroxyl group, p-methoxyphenol, hydroquinone, 2,6-dit-butyl-4-methylphenol or the like is used as a polymerization inhibitor, and a urethanization reaction catalyst. A method of using dibutyltin dilaurate, dibutyltin diacetate, tin octylate, zinc octylate and the like at a reaction temperature of 40 to 120 ° C., particularly 60 to 90 ° C. is preferable.

  Further, when the reactive group of the polymer (P1) is a glycidyl group and the functional group of the compound (c3) is a carboxyl group, or the reactive group of the polymer (P1) is a carboxyl group When the functional group of the compound (c3) is a glycidyl group, p-methoxyphenol, hydroquinone, 2,6-di-t-butyl-4-methylphenol or the like is used as a polymerization inhibitor, and esterification is performed. As reaction catalysts, tertiary amines such as triethylamine, quaternary ammoniums such as tetramethylammonium chloride, tertiary phosphines such as triphenylphosphine, and quaternary phosphoniums such as tetrabutylphosphonium chloride are used. The reaction is preferably carried out at a reaction temperature of 80 to 130 ° C, particularly 100 to 120 ° C.

  The organic solvent used in the above reaction is preferably ketones, esters, amides, sulfoxides, ethers, hydrocarbons, specifically, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, butyl acetate, Examples include propylene glycol monomethyl ether acetate, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, toluene, xylene and the like. These may be appropriately selected in consideration of the boiling point and compatibility.

  In order to produce the fluorine-containing polymerizable resin (C-2), first, a polymerizable unsaturated monomer (c2) having a reactive group is polymerized to produce a polymer (P2). At this time, as described above, other polymerizable unsaturated monomers may be used in combination with the polymerizable unsaturated monomer (c2) for copolymerization. As in the case of producing the polymer (P1), the polymerization method is carried out by adding a polymerizable unsaturated monomer having a reactive group (c2) and, if necessary, other polymerizable unsaturated monomer, a polymerization initiator. The method of using and polymerizing is mentioned. At this time, it is preferably carried out in the presence of an organic solvent, and a chain transfer agent may be used if necessary. The organic solvent, polymerization initiator, and chain transfer agent that can be used can be the same as those used for producing the polymer (P1).

  The polymer (P2) thus obtained has a number average by GPC measurement in that crosslinking insolubilization may occur during the reaction with the compound (c1 ′) if it is too high in molecular weight. The molecular weight is in the range of 800 to 3,000, in particular 1,000 to 2,000, and the weight average molecular weight is in the range of 1,200 to 6,000, in particular 1,500 to 4,000. It is preferable that

  Next, the obtained polymer (P2) has a poly (perfluoroalkylene ether) chain and a reactive group (polymerizable unsaturated monomer (c2) that the polymer (P2) has at both ends thereof. And a functional group capable of reacting with the reactive group of the polymer (P2) to form a chemical bond. And a compound (c3) containing a polymerizable unsaturated group are reacted to obtain the intended fluorine-containing polymerizable resin (C-2).

  At this time, the compound (c1 ′) may be reacted with the polymer (P2) first, and then the compound (c3) may be reacted, or vice versa. Further, the compound (c1 ′) and the compound (c3) may be reacted with the polymer (P2) at the same time.

  In addition, the effect of the present invention is remarkable by appropriately adjusting the amount of the reactive group in the polymer (P2) and the reaction ratio of the compound (c1 ′) and the compound (c3) to the reactive group. It is desirable from the point. Specifically, the amount of reactive groups in the polymer (P2) is 100 to 200 g / eq. In the range, the functional group concentration is high, and the antifouling property of the cured coating film is preferable, and the compound (c1 ′) with respect to 1 mol of the reactive group in the polymer (P2). ) In a ratio of 0.05 to 0.20 mol of functional groups, and 0.8 mol of functional groups in compound (c3) with respect to 1 mol of reactive groups in polymer (P2). The reaction is preferably carried out at a ratio of ˜0.95 mol.

  Here, the functional group in the compound (c1 ′) having a poly (perfluoroalkylene ether) chain and a functional group capable of reacting with the reactive group of the polymer (P2) at both ends thereof to form a chemical bond. Includes a hydroxyl group, an isocyanate group, a glycidyl group, a carboxyl group, and the like. For example, when the reactive group possessed by the polymer (P2) is a hydroxyl group, an isocyanate group is exemplified as the functional group possessed by the compound (c1 ′), and the reactive group possessed by the polymer (P2) is an isocyanate group. Is a hydroxyl group as the functional group of the compound (c1 ′), and when the reactive group of the polymer (P2) is a glycidyl group, the functional group of the compound (c1 ′) is A carboxyl group is mentioned, When the reactive group which a polymer (P2) has is a carboxyl group, a glycidyl group is mentioned as a functional group which a compound (c1 ') has.

  Examples of such compound (c1 ′) include compounds represented by the following structural formulas c1′-1 to c1′-6, or polyfunctional isocyanates such as hexamethylene diisocyanate and tolylene diisocyanate. And compounds modified with a bifunctional epoxy resin such as a bisphenol-type epoxy resin. In the following structural formulas, “—PFPE—” represents a poly (perfluoroalkylene ether) chain. Among these, those represented by the following structural formulas c1′-1 to c1′-6 are preferable. In particular, when the reactive group of the polymer (P2) is an isocyanate group, the following structural formula c1 ′ The compound (c1 ′) represented by −1 is preferable from the viewpoint of excellent reactivity with the reactive group.

  Moreover, the compound (c3) used here is synonymous with the compound (c3) used in the case of manufacture of above-mentioned fluorine-containing polymerizable resin (C-1).

  As described above, the reaction between the polymer (P2), the compound (c1 ′) and the compound (c3) is performed by reacting the polymer (P2) with the compound (c1 ′) and then reacting the compound (c3). Alternatively, after the polymer (P2) and the compound (c3) are reacted, the compound (c1 ′) may be reacted, or the compound (c1 ′) and the compound (c3) are simultaneously combined. You may make it react with unification | combination (P2). The reaction conditions can be appropriately selected depending on the type of functional group involved in the reaction, regardless of which method is used.

  For example, when one of the reactive group in the polymer (P2) and the functional group in the compound (c1 ′) is a hydroxyl group and the other is an isocyanate group, or the reactive group in the polymer (P2) And when one of the functional groups in the compound (c3) is a hydroxyl group and the other is an isocyanate group, p-methoxyphenol, hydroquinone, 2,6-di-t-butyl-4-methylphenol and the like as a polymerization inhibitor Is preferred, and dibutyltin dilaurate, dibutyltin diacetate, tin octylate, zinc octylate and the like are used as the urethanization reaction catalyst and the reaction is carried out at a reaction temperature of 40 to 120 ° C, particularly 60 to 90 ° C.

  Further, when one of the reactive group in the polymer (P2) and the functional group in the compound (c1 ′) is a carboxyl group and the other is a glycidyl group, or the reactivity in the polymer (P2) Group and one of the functional groups in the compound (c3) is a carboxyl group and the other is a glycidyl group, p-methoxyphenol, hydroquinone, 2,6-di-t-butyl-4-methyl as a polymerization inhibitor Using phenol or the like, tertiary ester such as triethylamine, quaternary ammonium such as tetramethylammonium chloride, tertiary phosphine such as triphenylphosphine, tetrabutylphosphonium chloride or the like as an esterification reaction catalyst It is preferable to use a quaternary phosphonium or the like and to react at a reaction temperature of 80 to 130 ° C., particularly 100 to 120 ° C.

  In these reactions, an organic solvent can be appropriately used. Examples of the organic solvent that can be used include ketones, esters, amides, sulfoxides, ethers, and hydrocarbons. 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 Etc. These may be appropriately selected in consideration of the boiling point and compatibility.

  The fluorine-containing polymerizable resin (C) represented by the fluorine-containing polymerizable resin (C-1) or the fluorine-containing polymerizable resin (C-2) described in detail above is the number of the fluorine-containing polymerizable resin (C). It is a gel at the time of manufacturing these resins that the average molecular weight (Mn) is in the range of 1,500 to 5,000 and the weight average molecular weight (Mw) is in the range of 4,000 to 50,000. It is preferable from the standpoint that the coating film performance that is highly cross-linked and excellent in antifouling property is exhibited without causing the deterioration.

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

(Polystyrene used)
“A-500” manufactured by Tosoh Corporation
"A-1000" manufactured by Tosoh Corporation
"A-2500" manufactured by Tosoh Corporation
"A-5000" manufactured by Tosoh Corporation
“F-1” manufactured by Tosoh Corporation
"F-2" manufactured by Tosoh Corporation
“F-4” manufactured by Tosoh Corporation
“F-10” manufactured by Tosoh Corporation
“F-20” manufactured by Tosoh Corporation
“F-40” manufactured by Tosoh Corporation
“F-80” manufactured by Tosoh Corporation
“F-128” manufactured by Tosoh Corporation
Sample: A 1.0 mass% tetrahydrofuran solution in terms of resin solid content filtered through a microfilter (100 μl).

  Moreover, it is preferable from the point of the antifouling property of a cured coating film that the said fluorine-containing polymeric resin (C) contains a fluorine atom in the ratio used as 2-25 mass% in this resin.

  Furthermore, the polymerizable unsaturated group content in the fluorine-containing polymerizable resin (C) is such that the 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 blending amount of the fluorine-containing polymerizable resin (C) in the active energy ray-curable resin composition of the present invention is 100 parts by mass of non-volatile content in the active energy ray-curable resin composition (the surface-modified silica and polymerization start It is preferable that it is 0.01-10 mass parts with respect to an agent. In particular, 0.05 to 3 parts by mass is preferable because the coating film surface can be efficiently modified without impairing physical properties such as the coating film hardness inherent to the resin composition to be added.

  The blending ratio (mass ratio) of the surface-modified silica particles and the fluorine-containing polymerizable resin (C) is preferably the former 30 to 95: the latter 70 to 5, and more preferably the former 50 to 90: the latter 50 to 10. The former 70 to 85: the latter 30 to 15 is more preferable. If the blending ratio of the surface-modified silica particles and the fluorine-containing polymerizable resin (C) is within this range, good antifouling properties can be obtained.

  Examples of the main component of the active energy ray-curable resin composition include a polymerizable monomer (D) and a polymerizable resin (E). These polymerizable monomer (D) and polymerizable resin (E) are preferably selected in accordance with the type of active energy ray polymerizable group possessed by the surface-modified silica. For example, when the active energy ray polymerizable group of the surface-modified silica is a radical polymerizable group such as a (meth) acryl group, a polymerizable monomer (D) having a radical polymerizable group such as a (meth) acryl group When the active energy ray polymerizable group of the surface-modified silica is a cationic polymerizable group such as a vinyl ether group, an epoxy group, or an oxetanyl group, the vinyl ether group, the epoxy group, the oxetanyl group, etc. It is preferable to use a polymerizable monomer (D) having a cationic polymerizable group and a polymerizable resin (E).

  Among the polymerizable monomers (D), examples of the monofunctional monomer having a radical polymerizable group include N-vinylcaprolactam, N-vinylpyrrolidone, N-vinylcarbazole, vinylpyridine, acrylamide, N, N-dimethyl ( (Meth) acrylamide, isobutoxymethyl (meth) acrylamide, t-octyl (meth) acrylamide, diacetone (meth) acrylamide, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, 7-amino-3,7-dimethyl Octyl (meth) acrylate, acryloylmorpholine, lauryl (meth) acrylate, dicyclopentadienyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentenyl (meth) acrylate Rate, tetrahydrofurfuryl (meth) acrylate, ethylene glycol (meth) acrylate, butoxyethyl (meth) acrylate, methyl triethylene diglycol (meth) acrylate, phenoxyethyl (meth) acrylate. These monofunctional monomers can be used alone or in combination of two or more.

  Among the polymerizable monomers (D), examples of the monofunctional monomer having a cationic polymerizable group include, for example, ethyl vinyl ether, 2-ethylhexyl vinyl ether, dodecyl vinyl ether, octadecyl vinyl ether, vinyl cyclohexyl ether, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether. , Diethylene glycol monovinyl ether, cyclohexanedimethanol monovinyl ether, 3-ethyl-3-hydroxyethyl oxetane, and the like. These monofunctional monomers can be used alone or in combination of two or more.

  Among the polymerizable monomers (D), examples of the polyfunctional monomer having a radical polymerizable group include trimethylolpropane tri (meth) acrylate, triethylene oxide-modified trimethylolpropane tri (meth) acrylate, and tripropylene oxide-modified glycerin. Tri (meth) acrylate, triethylene oxide-modified glycerol tri (meth) acrylate, triepichlorohydrin-modified glycerol tri (meth) acrylate, 1,3,5-triacroylhexahydro-s-triazine, tris (acryloyloxyethyl) ) Isocyanurate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, tetraethylene oxide modified pentaerythritol tetra (meth) acrylate Ditrimethylolpropane tetra (meth) acrylate, diethylene oxide modified ditrimethylolpropane tetra (meth) acrylate, alkyl modified dipentaerythritol pentaacrylate, alkyl modified dipentaerythritol tetraacrylate, ε-caprolactone modified dipentaerythritol hexa (meth) acrylate, Examples include dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexaethylene oxide-modified sorbitol hexa (meth) acrylate, hexakis (methacryloyloxyethyl) cyclotriphosphazene, and the like. These polyfunctional monomers can be used alone or in combination of two or more.

  Among the polymerizable monomers (D), examples of the polyfunctional monomer having a cationic polymerizable group include butanediol-1,4-divinyl ether, cyclohexane dimethanol divinyl ether, diethylene glycol divinyl ether, and dipropylene glycol divinyl ether. , Hexanediol divinyl ether, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, bis- (3,4-epoxycyclohexyl) adipate, diglycidyl ether of bisphenol A, diglycidyl ether of bisphenol F, water Diglycidyl ether of hydrogenated bisphenol A, diglycidyl ether of hydrogenated bisphenol F, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, etc. And the like. These polyfunctional monomers can be used alone or in combination of two or more.

  Among the polymerizable resins (E), those having a radical polymerizable group include an epoxy (meth) acrylate, an aliphatic polyisocyanate or an aromatic polyisocyanate obtained by reacting a compound having a plurality of epoxy groups with (meth) acrylic acid. Examples include urethane (meth) acrylate obtained by reacting isocyanate and (meth) acrylate having a hydroxyl group. These polymerizable resins (E) can be used alone or in combination of two or more.

  Examples of the epoxy (meth) acrylate include reacting (meth) acrylic acid 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. Can be mentioned.

  Examples of the aliphatic polyisocyanate used as a raw material for the urethane (meth) acrylate include tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, octamethylene diisocyanate, decamethylene diisocyanate, and 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 Diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated tetramethylxylylene diisocyanate, cyclohexyl diisocyanate, and the like.

  Examples of the aromatic polyisocyanate used as a raw material for the urethane (meth) acrylate include tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, xylylene diisocyanate, 1,5-naphthalene diisocyanate, tolidine diisocyanate, and p-phenylene. Diisocyanate etc. are mentioned.

  On the other hand, as the (meth) acrylate having a hydroxyl group used as a raw material for urethane (meth) acrylate, for example, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, pentanediol mono (meth) Mono (meth) acrylates of dihydric alcohols such as acrylate, hexanediol mono (meth) acrylate, neopentyl glycol mono (meth) acrylate, and hydroxypivalic acid neopentyl glycol mono (meth) acrylate; trimethylolpropane di (meth) acrylate , Ethoxylated trimethylolpropane (meth) acrylate, propoxylated trimethylolpropane di (meth) acrylate, glycerin di (meth) acrylate, di (meth) Mono- or di (meth) acrylates of trivalent alcohols such as acryloyloxyethyl-hydroxyethyl-isocyanurate, or mono- and di (meta) s having hydroxyl groups obtained by modifying some of these alcoholic hydroxyl groups with ε-caprolactone ) Acrylate; compound having one hydroxyl group and three or more (meth) acryloyl groups in one molecule such as pentaerythritol tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, etc. Or a polyfunctional (meth) acrylate in which the hydroxyl group of this compound is modified with ε-caprolactone; dipropylene glycol mono (meth) acrylate, diethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) (Meth) acrylate compounds having an oxyalkylene chain such as acrylate and polyethylene glycol mono (meth) acrylate; block structures such as polyethylene glycol-polypropylene glycol mono (meth) acrylate and polyoxybutylene-polyoxypropylene mono (meth) acrylate (Meth) acrylate compound having an oxyalkylene chain; having a random structure oxyalkylene chain such as poly (ethylene glycol-tetramethylene glycol) mono (meth) acrylate, poly (propylene glycol-tetramethylene glycol) mono (meth) acrylate A (meth) acrylate compound etc. are mentioned.

  The reaction of the above aliphatic polyisocyanate or aromatic polyisocyanate with the (meth) acrylate having a hydroxyl group can be carried out by a conventional method in the presence of a urethanization catalyst. Examples of the urethanization catalyst include amines such as pyridine, pyrrole, triethylamine, diethylamine and dibutylamine; phosphines such as triphenylphosphine and triethylphosphine; dibutyltin dilaurate, octyltin trilaurate, octyltin diacetate, dibutyltin diacetate Organic tin compounds such as acetate and tin octylate; organometallic compounds such as zinc octylate and the like.

  Among these urethane (meth) acrylate resins, those obtained by a reaction between an aliphatic polyisocyanate and a (meth) acrylate having a hydroxyl group are particularly preferred from the viewpoint of excellent transparency of the cured coating film and excellent curability.

  On the other hand, examples of the polymerizable monomer (D) having a cationic polymerizable group include phenol novolac type epoxy resins and cresol novolac type epoxy resins. These polymerizable resins (E) can be used alone or in combination of two or more.

  The active energy ray-curable resin composition of the present invention refers to a composition that cures when irradiated with active energy rays. The active energy rays refer to ionizing radiation such as ultraviolet rays, electron beams, α rays, β rays, and γ rays. When ultraviolet rays are used as the active energy rays, a photopolymerization initiator (F) is added to the active energy ray curable resin composition. If necessary, a photosensitizer is further added. On the other hand, when ionizing radiation such as electron beam, α-ray, β-ray, and γ-ray is used, it cures quickly without using a photopolymerization initiator or photosensitizer. There is no.

  As the photopolymerization initiator (F) when the active energy ray polymerizable group of each component contained in the active energy ray curable resin composition of the present invention is a radical polymerizable group, intramolecular cleavage type photopolymerization is initiated. And a hydrogen abstraction type photopolymerization initiator. 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. These photopolymerization initiators (F) can be used alone or in combination of two or more.

  On the other hand, as the photopolymerization initiator (F) when the active energy ray polymerizable group of each component contained in the active energy ray curable resin composition of the present invention is a cationic polymerizable group, for example, triallylsulfonium -Hexafluorophosphate salt, phosphorus aromatic sulfonium-hexafluorophosphate salt, phosphorus aromatic sulfonium-hexafluoroantimony salt, diallyl iodonium salt and the like. 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 the like.

  These photopolymerization initiators and photosensitizers are preferably used in an amount of 0.01 to 20 parts by weight, more preferably 0. 0 parts by weight with respect to 100 parts by weight of the nonvolatile component in the active energy ray-curable resin composition. 3 to 10 parts by mass.

  Furthermore, the active energy ray-curable resin composition of the present invention can be used for adjusting the viscosity and refractive index, or adjusting 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. Other compounding materials for the purpose of adjusting other paint properties and coating film properties include, for example, various organic solvents, acrylic resins, phenol resins, polyester resins, urethane resins, urea resins, melamine resins, alkyd resins, epoxy resins, polyamides. Various resins such as resin, polycarbonate resin, petroleum resin, fluororesin, PTFE (polytetrafluoroethylene), polyethylene, carbon, titanium oxide, alumina, copper, silica fine particles, etc., polymerization initiator, polymerization Inhibitors, antistatic agents, antifoaming agents, viscosity modifiers, light stabilizers, weathering stabilizers, heat stabilizers, antioxidants, rust prevention , Slip agents, waxes, luster modifiers, mold release agents, compatibilizers, conductive modifiers, pigments, dyes, dispersing agents, dispersion stabilizers, silicone-based, may be used in combination hydrocarbon surfactants.

  It is useful to use the organic solvent in the above-described blending component as a dilution solvent for adjusting the viscosity in order to impart coating suitability to the substrate. Examples of the diluent solvent include aromatic hydrocarbons such as toluene and xylene; alcohols such as methanol, ethanol and isopropyl alcohol; esters such as ethyl acetate and propylene glycol monomethyl ether acetate; methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone. Examples include ketones. These solvents can be used alone or in combination of two or more.

  Examples of the substrate on which the active energy ray-curable resin composition of the present invention is applied include, for example, a plastic substrate; a ceramic substrate such as glass; and a metal substrate (including metal plating) such as iron and aluminum. And is particularly useful for plastic substrates. Examples of the plastic substrate material include polyester resins such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate; polyolefin resins such as polypropylene, polyethylene, and polymethylpentene-1; and cellulose resins such as triacetyl cellulose; Examples thereof include polystyrene resin, polyamide resin, polycarbonate resin, norbornene resin, modified norbornene resin, and cyclic olefin copolymer. Moreover, what combined 2 or more types of base materials which consist of these resin may be used. The shape of these plastic substrates is not particularly limited, and the active energy ray-curable resin composition of the present invention can be used as long as it is a normal molded product, but a film or sheet is preferred.

  Examples of the method for applying the active energy ray-curable resin composition of the present invention to a substrate include gravure coating, roll coating, comma coating, air knife coating, kiss coating, spray coating, transfer coating, dip coating, spinner coating, Examples include wheeler coating, brush coating, solid coating by silk screen, wire bar coating, and flow coating. Also, printing methods such as offset printing and letterpress printing may be used. Among these, gravure coating, roll coating, comma coating, air knife coating, kiss coating, wire bar coating, and flow coating are preferable because a coating film having a more constant thickness can be obtained.

  Examples of the active energy ray for curing the active energy ray-curable resin composition of the present invention include active energy rays such as light, electron beam, and radiation. Specific energy sources or curing devices include, for example, germicidal lamps, ultraviolet fluorescent lamps, carbon arc, xenon lamps, high pressure mercury lamps for copying, medium or high pressure mercury lamps, ultrahigh pressure mercury lamps, electrodeless lamps, metal halide lamps, natural light, etc. Or an electron beam using a scanning type or curtain type electron beam accelerator.

  Among these, the active energy ray is preferably ultraviolet rays, and irradiation with an inert gas atmosphere such as nitrogen gas is more preferable from the viewpoint of increasing the polymerization efficiency. Further, if necessary, heat may be used as an energy source, and heat treatment may be performed after curing by irradiation with active energy rays.

  As an article having a cured coating film of the active energy ray-curable resin composition of the present invention, for example, a protective film requiring fingerprint resistance; used for flat panel displays such as liquid crystal displays, plasma displays, and organic EL displays. Examples thereof include an antireflection film and an antiglare film.

  Further, a protective film for a polarizing plate of a liquid crystal display typified by a triacetyl cellulose (TAC) film, a color filter of a liquid crystal display using the active energy ray-curable resin composition of the present invention as a black matrix, a touch panel, a mobile phone Cases and mobile phone liquid crystal displays are also included.

  Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples.

(Synthesis Example 1) Synthesis of an alkoxysilane having a polydimethylsiloxane chain Polydimethylsiloxane having a hydroxyl group ("Silaplane FM-0421" manufactured by Chisso Corporation), molecular weight in a glass flask equipped with a stirrer, a cooling tube and a thermometer 5,000) 95.3 parts by mass and 4.7 parts by mass of 3-isocyanatopropyltriethoxysilane (“KBE-9007” manufactured by Shin-Etsu Chemical Co., Ltd.) were charged and heated to 80 ° C. Thereafter, 0.02 part by mass of tin octylate was added, followed by reaction at 80 ° C. for 8 hours to obtain alkoxysilane (A-1) having a polydimethylsiloxane chain. The end point of the reaction was determined when the infrared absorption spectrum of the reaction product was measured and the isocyanate group absorption spectrum was 0.1% or less.

(Synthesis Example 2)
A glass flask equipped with a stirrer, a thermometer, a cooling tube, and a dropping device is charged with 20 masses of a hydroxyl group-containing perfluoropolyether compound having 25 to 80 fluorine atoms represented by the following structural formula (X-1). 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, start stirring under an air stream, While maintaining the temperature at 10 ° C., 2.7 parts of acrylic acid chloride was added dropwise over 1 hour. After completion of dropping, the mixture is stirred at 10 ° C. for 1 hour, heated to 30 ° C. for 1 hour, then heated to 50 ° C. and stirred for 10 hours, and acrylic acid is measured by gas chromatography. The disappearance of chloride was confirmed. Next, after adding 40 parts by mass of diisopropyl ether as a solvent, 80 parts by mass of ion-exchanged water was mixed and stirred, and then left to stand to separate and remove the aqueous layer, and washing was repeated 3 times. Subsequently, 0.02 parts by mass of p-methoxyphenol was added as a polymerization inhibitor, 8 parts by mass of magnesium sulfate was added as a dehydrating agent, and the mixture was allowed to stand for 1 day for complete dehydration, and then the dehydrating agent was filtered off. .

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

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

  Subsequently, 21.5 mass parts of monomers (c1-1-1) represented by the following structural formula (c1-1-1) were obtained by distilling a solvent off under reduced pressure.

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

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

  Next, 63 parts by mass of methyl isobutyl ketone (hereinafter referred to as “MIBK”) as a solvent was charged in another glass flask equipped with a stirrer, a thermometer, a condenser, and a dropping device while stirring under a nitrogen stream. The temperature was raised to 105 ° C. Subsequently, 21.5 parts by mass of the monomer (c1-1-1) obtained above, 41.3 parts by mass of 2-hydroxyethyl methacrylate, and t-butylperoxy-2-ethylhexanoate 9 as a polymerization initiator 4 parts by weight and 35.4 parts by weight of an initiator solution mixed with 126 parts by weight of MIBK as a solvent were set in separate dropping devices, and the flask was kept at 105 ° C for 2 hours at the same time. It was dripped. After completion of the dropwise addition, the mixture was stirred at 105 ° C. for 10 hours, and then the solvent was distilled off under reduced pressure, whereby an 84 mass% MIBK solution of the polymer (c1-1) (63.7 as the polymer (c1-1)) was obtained. Containing parts by mass).

  Next, 107.5 parts by mass of methyl ethyl ketone (hereinafter referred to as “MEK”) as a solvent, 0.04 parts by mass of p-methoxyphenol as a polymerization inhibitor, 0.3 part by mass of dibutylhydroxytoluene as an antioxidant, a urethanization catalyst As a starting material, 0.03 part by mass of tin octylate was charged, stirring was started under an air stream, and 43.9 parts by mass of 2-acryloyloxyethyl isocyanate was added dropwise over 1 hour while maintaining 60 ° C. After completion of the dropwise addition, the mixture was stirred at 60 ° C. for 1 hour, then heated to 80 ° C. and stirred for 10 hours. As a result, the disappearance of the isocyanate group was confirmed by IR spectrum measurement. Next, MEK was added so that the fluorine-containing polymerizable resin (C1) was 40% by mass to obtain a MEK solution of the fluorine-containing polymerizable resin (C1). As a result of measuring the molecular weight of the obtained fluorine-containing polymerizable resin by GPC (polystyrene equivalent molecular weight), the number average molecular weight was 2,400, the weight average molecular weight was 7,100, and the maximum molecular weight was 200,000.

Example 1
In a glass flask equipped with a stirrer, a condenser, and a thermometer, a MEK dispersion of silica particles (“MEK-ST” manufactured by Nissan Chemical Industries, Ltd., average particle size: 10 to 20 nm, shape: spherical, silica content: 30 parts by mass) 100 parts by mass, 0.1 parts by mass of an antioxidant (dibutylhydroxytoluene) and 0.01 parts by mass of a polymerization inhibitor (p-methoxyphenol) were charged and the temperature was raised to 70 ° C., then Synthesis Example 1 0.9 parts by mass of alkoxysilane (A-1) having a polydimethylsiloxane chain obtained in 1 above was added and reacted at 70 ° C. for 1 hour. Next, 8.45 parts by mass of 3-acryloxypropyltrimethoxysilane (“KBM-5103” manufactured by Shin-Etsu Chemical Co., Ltd.) was added and reacted at 70 ° C. for 4 hours to obtain surface-modified silica (S-1). It was.

(Example 2)
Surface-modified silica (S-2) was obtained in the same manner as in Example 1 except that 0.9 part by mass of alkoxysilane (A-1) having a polydimethylsiloxane chain was changed to 1.8 parts by mass.

(Example 3)
MEK dispersion of silica particles (“MEK-ST” manufactured by Nissan Chemical Industries, Ltd.) 100 parts by mass MEK dispersion of silica particles (“MEK-ST-L” manufactured by Nissan Chemical Industries, Ltd., average particle diameter 40 nm, shape) : Spherical, silica content: 30% by mass) Surface-modified silica (S-3) was obtained in the same manner as in Example 1 except that the amount was changed to 100 parts by mass.

(Comparative Example 1)
In a glass flask equipped with a stirrer, a condenser, and a thermometer, 100 parts by mass of silica particle MEK dispersion (“MEK-ST” manufactured by Nissan Chemical Industries, Ltd.), 0.1 mass of antioxidant (dibutylhydroxytoluene) And 0.01 parts by mass of a polymerization inhibitor (p-methoxyphenol) were charged, and the temperature was raised to 70 ° C. Next, 8.45 parts by mass of 3-acryloxypropyltrimethoxysilane (“KBM-5103” manufactured by Shin-Etsu Chemical Co., Ltd.) was added and reacted at 70 ° C. for 4 hours to obtain surface-modified silica (S-4). It was.

(Comparative Example 2)
In a glass flask equipped with a stirrer, a condenser, and a thermometer, 100 parts by mass of silica particle MEK dispersion (“MEK-ST” manufactured by Nissan Chemical Industries, Ltd.), 0.1 mass of antioxidant (dibutylhydroxytoluene) And 0.01 parts by mass of a polymerization inhibitor (p-methoxyphenol) were charged, and the temperature was raised to 70 ° C. Next, 0.9 part by mass of alkoxysilane (A-1) having a polydimethylsiloxane chain obtained in Synthesis Example 1 was added and reacted at 70 ° C. for 1 hour to obtain surface-modified silica (S-5). .

(Preparation of active energy ray-curable resin composition)
Using the surface-modified silica (S-1) to (S-5) obtained in Examples 1 to 3 and Comparative Examples 1 and 2, and the fluorine-containing polymerizable resin (C1) obtained in Synthesis Example 2 The active energy ray-curable resin composition was prepared as follows.

Example 4
50 parts by mass of pentafunctional non-yellowing urethane acrylate (hereinafter referred to as “polyfunctional urethane acrylate”), 50 parts by mass of dipentaerythritol hexaacrylate (hereinafter referred to as “DPHA”), 25 parts by mass of butyl acetate, photopolymerization started 5 parts by mass of an agent (“Irgacure 184” manufactured by Ciba Specialty Chemicals Co., Ltd., 1-hydroxycyclohexyl phenyl ketone) and 124 parts by mass of MEK were mixed and dissolved, and then the surface-modified silica obtained in Example 1 (S-1 14 parts by mass (5.04 parts by mass as surface-modified silica) was added and mixed uniformly to obtain 268 parts by mass of an active energy ray-curable resin composition.

(Example 5)
50 parts by mass of polyfunctional urethane acrylate, 50 parts by mass of DPHA, 25 parts by mass of butyl acetate, 5 parts by mass of photopolymerization initiator (“Irgacure 184”, 1-hydroxycyclohexyl phenyl ketone, manufactured by Ciba Specialty Chemicals Co., Ltd.) and 124 parts by mass of MEK After mixing and dissolving, 14 parts by mass of a 36% by mass MEK solution of the surface-modified silica (S-2) obtained in Example 2 (5.04 parts by mass as surface-modified silica) was added and mixed uniformly. 268 mass parts of active energy ray hardening-type resin compositions were obtained.

(Example 6)
50 parts by mass of polyfunctional urethane acrylate, 50 parts by mass of DPHA, 25 parts by mass of butyl acetate, 5 parts by mass of photopolymerization initiator (“Irgacure 184”, 1-hydroxycyclohexyl phenyl ketone, manufactured by Ciba Specialty Chemicals Co., Ltd.) and 124 parts by mass of MEK After mixing and dissolving, 14 parts by mass of a 36% by mass MEK solution of surface-modified silica (S-3) obtained in Example 3 (5.04 parts by mass as surface-modified silica) was added and mixed uniformly. 268 mass parts of active energy ray hardening-type resin compositions were obtained.

(Example 7)
49 parts by mass of polyfunctional urethane acrylate, 49 parts by mass of DPHA, 25 parts by mass of butyl acetate, 5 parts by mass of photopolymerization initiator (“Irgacure 184”, 1-hydroxycyclohexyl phenyl ketone, manufactured by Ciba Specialty Chemicals Co., Ltd.) and 123 parts by mass of MEK After mixing and dissolving, 14 parts by mass of a 36% by mass MEK solution of surface-modified silica (S-1) obtained in Example 1 (5.04 parts by mass as surface-modified silica) was added and mixed uniformly. Further, 3 parts by mass of a 40% by mass solution of the fluorine-containing polymerizable resin (C1) obtained in Synthesis Example 5 (solvent composition: MEK / MIBK = 93/7, 1.2% by mass as the fluorine-containing polymerizable resin (C1)) Part) was added and mixed uniformly to obtain 268 parts by mass of an active energy ray-curable resin composition.

(Example 8)
50 parts by mass of polyfunctional urethane acrylate, 50 parts by mass of DPHA, 25 parts by mass of butyl acetate, 5 parts by mass of a photopolymerization initiator (“Irgacure 184”, 1-hydroxycyclohexyl phenyl ketone, manufactured by Ciba Specialty Chemicals Co., Ltd.) and 123 parts by mass of MEK After mixing and dissolving, 14 parts of a 36% by mass MEK solution of surface-modified silica (S-1) obtained in Example 1 (5.04 parts by mass as surface-modified silica) was added and mixed uniformly, Furthermore, 1 part by mass of a 40% by mass solution of the fluorine-containing polymerizable resin (C1) obtained in Synthesis Example 5 (solvent composition: MEK / MIBK = 93/7, 0.4 parts by mass as the fluorine-containing polymerizable resin (C1)) ) Was added and mixed uniformly to obtain 268 parts by mass of an active energy ray-curable resin composition.

(Comparative Example 3)
53 parts by mass of polyfunctional urethane acrylate, 53 parts by mass of DPHA, 26 parts by mass of butyl acetate, 5 parts by mass of photopolymerization initiator (“Irgacure 184”, 1-hydroxycyclohexyl phenyl ketone, manufactured by Ciba Specialty Chemicals Co., Ltd.) and 131 parts by mass of MEK Were mixed and uniformly dissolved to obtain 268 parts by mass of an active energy ray-curable resin composition.

(Comparative Example 4)
50 parts by mass of polyfunctional urethane acrylate, 50 parts by mass of DPHA, 25 parts by mass of butyl acetate, 5 parts by mass of photopolymerization initiator (“Irgacure 184”, 1-hydroxycyclohexyl phenyl ketone, manufactured by Ciba Specialty Chemicals Co., Ltd.) and 124 parts by mass of MEK After mixing and dissolving, 14 parts by mass of a 36% by mass MEK solution of surface-modified silica (S-4) obtained in Comparative Example 1 (5.04 parts by mass as surface-modified silica) was added and mixed uniformly. 268 mass parts of active energy ray hardening-type resin compositions were obtained.

(Comparative Example 5)
50 parts by mass of polyfunctional urethane acrylate, 50 parts by mass of DPHA, 25 parts by mass of butyl acetate, 5 parts by mass of a photopolymerization initiator (“Irgacure 184”, 1-hydroxycyclohexyl phenyl ketone, manufactured by Ciba Specialty Chemicals Co., Ltd.) and 123 parts by mass of MEK After mixing and dissolving, 15 parts by mass of a 34% by mass MEK solution of surface modified silica (S-5) obtained in Comparative Example 2 (5.1 parts by mass as surface modified silica) was added and mixed uniformly. 268 mass parts of active energy ray hardening-type resin compositions were obtained.

(Comparative Example 6)
52 parts by mass of polyfunctional urethane acrylate, 52 parts by mass of DPHA, 26 parts by mass of butyl acetate, 5 parts by mass of photopolymerization initiator (“Irgacure 184”, 1-hydroxycyclohexyl phenyl ketone, manufactured by Ciba Specialty Chemicals Co., Ltd.) and 130 parts by mass of MEK After mixing and dissolving, 3 parts by mass of a 40% by mass solution of the fluorine-containing polymerizable resin (C1) obtained in Synthesis Example 2 (solvent composition: MEK / MIBK = 93/7, fluorine-containing polymerizable resin (C1) As 1.2 parts by mass) and mixed uniformly to obtain 268 parts by mass of an active energy ray-curable resin composition.

[Evaluation of active energy ray-curable resin composition]
(Preparation of sample for evaluation)
The ultraviolet curable resin composition containing the surface-modified silica particles obtained above was applied to a polyethylene terephthalate (PET) film (thickness: 188 μm) using a bar coater (No. 13), and then dried at 60 ° C. It was put into a machine for 5 minutes to evaporate the solvent, and cured using an ultraviolet curing device (in a nitrogen atmosphere, using a high pressure mercury lamp, an ultraviolet irradiation amount of ² kJ / m ² ) to produce a coated film. Further, as Comparative Example 4, a coating film was similarly prepared for an ultraviolet curable resin composition to which no fluorine-containing polymerizable copolymer was added. Immediately after the coating, the following dirt adhesion prevention evaluation was performed at room temperature for 1 day, and then the following contact angles were measured and evaluated.

(Measurement and evaluation of contact angle)
The water and n-dodecane contact angles on the coated surface of the coated film obtained above were measured to evaluate water repellency and oil repellency. The contact angle was evaluated according to the following criteria.
(1) Water A: The contact angle is 100 ° or more.
B: The contact angle is 85 ° or more and less than 100 °.
C: The contact angle is less than 85 °.
(2) n-dodecane A: The contact angle is 50 ° or more.
B: The contact angle is 25 ° or more and less than 50 °.
C: The contact angle is less than 25 °.

(Evaluation of dirt adhesion prevention)
After drawing a line with an oil-based felt pen ("Magic Ink Large Black" manufactured by Teranishi Chemical Industry Co., Ltd.) on the coating surface of the coating film obtained above, wipe the ink with tissue paper multiple times. The process was repeated until 50% or more of the drawn ink area was not repelled. The number of repetitions of 50% or more of the area of the drawn ink was used as the number of repetitions, and the antifouling property was evaluated according to the following criteria.
AA: The number of repetitions is 20 or more.
A: The number of repetitions is 10 times or more and less than 20 times.
B: The number of repetitions is 5 times or more and less than 10 times.
C: The number of repetitions is less than 5.

  Tables 1 and 2 show the contents and evaluation results of the active energy ray-curable resin compositions obtained in Examples 4 to 8 and Comparative Examples 3 to 6. In the table, “PDMS” represents “polydimethylsiloxane”.

  It was found that the active energy ray-curable resin compositions of Examples 4 to 8 using the surface-modified silica of the present invention shown in Table 1 have a high antifouling property. Moreover, it turned out that Example 7 and 8 which used surface modification silica and fluorine-containing polymeric resin together has still higher dirt adhesion prevention property.

  On the other hand, the following was found from the evaluation results of the active energy ray-curable resin compositions of Comparative Examples 3 to 6 shown in Table 2.

  Although the active energy ray-curable resin composition of Comparative Example 3 was an example in which surface-modified silica was not blended, it was found that the antifouling property was insufficient. In addition, the active energy ray-curable resin composition of Comparative Example 6 is an example in which only the fluorine-containing polymerizable resin is blended without blending the surface-modified silica, but it is found that the antifouling property is insufficient. It was.

  The active energy ray-curable resin composition of Comparative Example 4 is an example in which silica having a surface modified only with an active energy ray polymerizable group was blended, but it was found that the antifouling property was insufficient. Moreover, although the active energy ray hardening-type resin composition of the comparative example 5 is an example which mix | blended the silica which surface-modified only the polydimethylsiloxane chain | strand, it turned out that stain | pollution | contamination prevention property is inadequate.

Claims (5)

On the surface of the silica particles via a silyloxy group, polyalkyl siloxane chain or polyaryl siloxane chain and a front surface-modified silica particles obtained by modifying the active energy ray-polymerizable group, the polymer structure of the polymerizable unsaturated monomer (Α) and a poly (perfluoroalkylene ether) chain (β), and a plurality of the polymer structures (α) are knotted through the poly (perfluoroalkylene ether) chain (β), An active energy ray-curable resin composition comprising a fluorine-containing polymerizable resin having a resin structure having an active energy ray polymerizable group in a side chain of the polymer structure (α). The active energy ray-curable resin composition according to claim 1, wherein the polyalkylsiloxane chain is a polydimethylsiloxane chain, and the active energy ray polymerizable group is a (meth) acryloyl group. The active energy ray-curable resin composition according to claim 2, wherein the polydimethylsiloxane chain has a molecular weight of 1,000 to 10,000. A cured product obtained by curing the active energy ray-curable resin composition according to claim 1. An article having a coating film obtained by curing the active energy ray-curable resin composition according to any one of claims 1 to 3 .