JP2013095817A - Alkoxysilane condensate and active energy ray-curable composition using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an alkoxysilane condensate capable of imparting high antifouling property and an active energy ray-curable composition containing the alkoxysilane condensate, and to also provide a cured product of the active energy ray-curable composition and an article with a cured coating film of the active energy ray-curable composition.SOLUTION: The active energy ray-curable composition contains the alkoxysilane condensate obtained by condensing an alkoxysilane (A) having a polyalkylsiloxane chain or a polyarylsiloxane chain and an alkoxysilane (B) having an active energy ray-polymerizable group. The active energy ray-curable composition may contain a fluorine-containing polymerizable resin (C) having a poly(perfluoroalkylene ether) chain and an active energy ray-polymerizable group in addition to the alkoxysilane condensate.

Description

  The present invention relates to an alkoxysilane condensate capable of imparting antifouling properties to a coating film and an active energy ray-curable composition containing the alkoxysilane condensate.

  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 an alkoxysilane condensate capable of imparting high antifouling properties and an active energy ray-curable composition containing the alkoxysilane condensate. Moreover, it is providing the articles | goods which have the hardened | cured material of this active energy ray hardening-type composition, and the hardened | cured coating film.

  As a result of diligent research, the inventors of the present invention have obtained an alkoxysilane condensation obtained by condensing an alkoxysilane having a polyalkylsiloxane chain or the like and an alkoxysilane having an active energy ray polymerizable group such as a (meth) acryloyl group. By using the product, it was found that an active energy ray-curable composition excellent in antifouling property was obtained, and the present invention was completed.

  That is, the present invention relates to an alkoxysilane condensate obtained by condensing an alkoxysilane (A) having a polyalkylsiloxane chain or a polyarylsiloxane chain and an alkoxysilane (B) having an active energy ray polymerizable group, and the alkoxysilane. The present invention relates to an active energy ray-curable composition containing a condensate. The present invention also relates to an article having a cured product of the active energy ray-curable composition and a cured coating film.

  The alkoxysilane condensate 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 composition containing the alkoxysilane condensate of the present invention is a protective film that requires antifouling properties, and an antireflection film used for FPDs such as liquid crystal displays, plasma displays, and organic EL displays. It is useful for anti-glare films. In particular, by applying the active energy ray-curable 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. It is.

  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.

1 is a GPC chart of the alkoxysilane condensate (1) obtained in Example 1. FIG.

  The alkoxysilane condensate of the present invention is obtained by condensing an alkoxysilane (A) having a polyalkylsiloxane chain or a polyarylsiloxane chain and an alkoxysilane (B) having an active energy ray polymerizable group.

  Examples of the alkoxysilane (A) used as a raw material for the alkoxysilane condensate of the present invention include, for example, an alkoxysilane having a reactive group (generally referred to as a silane coupling agent; hereinafter, “compound (a1)”. And a compound obtained by a method of reacting a functional group capable of forming a chemical bond with the reactive group and a compound (a2) having a polyalkylsiloxane chain or a polyarylsiloxane chain. It is done.

  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.

  Moreover, examples of the active energy ray polymerizable group of the alkoxysilane (B) that is a raw material of the alkoxysilane condensate of the present invention include a vinyl group, a (meth) acryl group, a vinyl ether group, an epoxy group, and an oxetanyl group. It is done. 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.

  Further, as the alkoxysilane (B), an alkoxysilane having a reactive group (hereinafter abbreviated as “compound (b1)”), a functional group capable of reacting with the reactive group to form a chemical bond, and activity. You may use what is obtained by making the compound (b2) which has an energy-beam polymeric group react.

  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 alkoxysilane condensate of the present invention can be obtained by condensing the alkoxysilane (A) and the alkoxysilane (B). The conditions for the condensation reaction include mixing and heating in the presence of water. Is mentioned. At this time, it is preferable to carry out the reaction under conditions where the active energy ray-curable group in the alkoxysilane (B) is not polymerized. For example, the reaction is preferably carried out by adjusting the temperature condition in the range of 30 to 120 ° C. This reaction is preferably carried out in the presence of a catalyst or a polymerization inhibitor, and if necessary in the presence of an organic solvent.

  The amount of water present is within a range of 0.4 to 10 moles of water molecules with respect to a total of 1 mole of alkoxy groups bonded to silicon atoms contained in the alkoxysilane (A) and the alkoxysilane (B). It is preferable to use it, it is more preferable to use it in the range of 0.45-1 mol, and it is especially preferable to use it in the range of 0.5-0.6 mol.

  Examples of the catalyst include inorganic acids such as hydrochloric acid, sulfuric acid and phosphoric acid; organic acids such as p-toluenesulfonic acid, monoisopropyl phosphate and acetic acid; inorganic bases such as sodium hydroxide and potassium hydroxide; tetraisopropyl titanate and tetrabutyl. Titanates such as titanate; 1,8-diazabicyclo [5.4.0] undecene-7 (DBU), 1,5-diazabicyclo [4.3.0] nonene-5 (DBN), 1,4-diazabicyclo [2.2.2] Compounds containing basic nitrogen atoms such as octane (DABCO), tri-n-butylamine, dimethylbenzylamine, monoethanolamine, imidazole, 1-methylimidazole; tetramethylammonium salt, tetrabutyl Quaternary ammonium salts such as ammonium salts and dilauryl dimethyl ammonium salts Counterions of these quaternary ammonium salts include chloride, bromide, carboxylate or hydroxide, etc.); dibutyltin diacetate, dibutyltin dioctoate, dibutyltin dilaurate, dibutyltin diacetylacetonate, tin octylate, Examples thereof include tin carboxylates such as tin stearate. These catalysts can be used alone or in combination of two or more.

  The catalyst is preferably used in a range of 0.0001 to 10% by mass, and in a range of 0.001 to 5% by mass with respect to the total amount of the alkoxysilane (A) and the alkoxysilane (B). It is more preferable to use in the range of 0.01 to 3% by mass.

  The polymerization inhibitor is not particularly limited, and examples thereof include p-methoxyphenol, hydroquinone, 2,6-di-t-butyl-4-methylphenol and the like.

  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 active energy ray-curable composition of the present invention is an active energy ray-curable composition containing the above alkoxysilane condensate. The compounding amount of the alkoxysilane condensate is 0.5 to 100 parts by mass of the nonvolatile content in the active energy ray-curable composition (excluding the polymerization initiator and the fluorine-containing polymerizable resin (C) described later). It is preferable that it is 30 mass parts. 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.

  In addition to the above alkoxysilane condensate, the active energy ray-curable composition of the present invention contains a fluorine-containing polymerizable resin (C) having a poly (perfluoroalkylene ether) chain and an active energy ray polymerizable group. It is preferable because antifouling properties are further improved.

  The fluorine-containing polymerizable resin (C) used in the present invention has a poly (perfluoroalkylene ether) chain and an active energy ray-curable group. The fluorine-containing polymerizable resin (C) used in the present invention has a poly (perfluoroalkylene ether) chain, so that the fluorine-containing polymerizable resin (C) is segregated on the coating film surface due to its low surface free energy. In addition, it has a high antifouling property due to the water / oil repellency of the poly (perfluoroalkylene ether) structure, and further exhibits high slipperiness, thereby improving the scratch resistance of the cured coating film. In addition, since the fluorine-containing polymerizable resin (C) has an active energy ray-curable group, the fluorine-containing polymerizable resins (C), or a polymerizable monomer (D) and a polymerizable resin (E) described later are included. To form a cured coating film, the poly (perfluoroalkylene ether) chain can be fixed to the cured coating film by a covalent bond, and the antifouling property of the cured coating film surface can be stabilized. Since the crosslink density on the film surface is increased, the scratch resistance can also be improved.

  Examples of the fluorine-containing polymerizable resin (C) include a poly (perfluoroalkylene ether) chain, a compound (c1) having a polymerizable unsaturated group at both ends thereof, and a polymerizable group having a reactive functional group (R1). A functional group (R2) having reactivity to the functional group (R1) and an active energy into a polymer (P1) obtained by copolymerizing a saturated monomer (c2) as an essential monomer component Examples thereof include a fluorine-containing polymerizable resin (C1) obtained by reacting a compound (c3) having a linear curable group. Further, a polymer (P2) of a polymerizable unsaturated monomer (c2) having a reactive functional group (R1), a poly (perfluoroalkylene ether) chain and the reactive functional group (R1) at both ends thereof. Compound (c1 ′) having functional group (R2) having reactivity with respect to, compound having functional group (R2) reactive to functional group (R1) and active energy ray-curable group Examples also include a fluorine-containing polymerizable resin (C2) obtained by reacting with (c3).

  Here, examples of the polymerizable unsaturated monomer (c2) include acrylic monomers, aromatic vinyl monomers, vinyl ester monomers, maleimide monomers, and the like. Examples of the reactive functional group (R1) possessed by the polymerizable unsaturated monomer (c2) include a hydroxyl group, an isocyanate group, an epoxy group, and a carboxyl group.

  Specific examples of 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 (meta) ) Acrylate, polypropylene glycol mono (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2- (meth) acryloyloxyethyl-2-hydroxyethyl phthalate, terminal hydroxyl group-containing lactone modification (meth) ) Hydroxyl-containing unsaturated monomers such as acrylate; 2- (meth) acryloyloxyethyl isocyanate, 2- (2- (meth) acryloyloxyethoxy) ethyl isocyanate, 1,1-bis ((meth) acryloyloxymethyl) Isocyanate group-containing unsaturated monomers such as ethyl isocyanate; Epoxy group-containing unsaturated monomers such as glycidyl methacrylate and 4-hydroxybutyl acrylate glycidyl ether; (meth) acrylic acid, 2- (meth) acryloyloxyethyl succinate Examples thereof include carboxyl group-containing unsaturated monomers such as acid, 2- (meth) acryloyloxyethylphthalic acid, and itaconic acid.

  The polymerizable unsaturated monomer (c2) may be copolymerized with other polymerizable unsaturated monomers. Other polymerizable unsaturated monomers include, for example, 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) acrylic (Meth) acrylic acid esters such as 2-ethylhexyl acid, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate; poly (Meth) acrylic acid esters having a silicone chain such as a dimethylsiloxane chain; styrene, α-methylstyrene, p-methylstyrene And aromatic vinyls such as p-methoxystyrene; maleimides such as maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, cyclohexylmaleimide, etc. Can be mentioned.

  In addition, the molecular weight of the silicone chain which (meth) acrylic acid ester which has the said silicone chain has the preferable range of 2,000-10,000. Moreover, when the (meth) acrylic acid ester having this silicone chain is used as another polymerizable unsaturated monomer, there is an effect that the slipperiness of the coating film surface is improved and the scratch resistance is improved. However, since the dirt wiping property is slightly lowered, it is preferably used as appropriate when the scratch resistance is more important than the dirt wiping property.

  Next, the poly (perfluoroalkylene ether) chain of the compound (c1) or the compound (c1 ′) is specifically composed of alternately divalent fluorocarbon groups having 1 to 3 carbon atoms and oxygen atoms. The thing which has the structure which connected is mentioned. The divalent fluorocarbon 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 (c4) Can be mentioned.

（上記構造式（ｃ４）中、Ｘは下記構造式（ｃ４−１）〜（ｃ４−５）であり、構造式（ｃ４）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 structural formula (c4), X is the following structural formulas (c4-1) to (c4-5), and all X in the structural formula (c4) may have the same structure, In addition, a plurality of structures may be present randomly or in a block shape, and n is a number of 1 or more representing a repeating unit.

  Among these, the perfluoromethylene structure represented by the structural formula (c4-1) and the structure in that the coating film surface is excellent in wiping off dirt on the surface and excellent in antifouling properties. Those coexisting with the perfluoroethylene structure represented by the formula (c4-2) are particularly preferable. Here, the abundance ratio between the perfluoromethylene structure represented by the structural formula (c4-1) and the perfluoroethylene structure represented by the structural formula (c4-2) is a molar ratio [structure (c4- 1) / structure (c4-2)] is preferably 1/10 to 10/1 in terms of antifouling property, and the value of n in the structural formula (c1) is 3 to 3. The range of 100 is preferable, the range of 6 to 70 is more preferable, and the range of 12 to 50 is more preferable.

  The poly (perfluoroalkylene ether) chain is a poly (perfluoroalkylene ether) chain because it has excellent antifouling properties such as fingerprint wiping properties and slipperiness, and is easy to improve compatibility with other components in the antireflection coating composition. Perfluoroalkylene ether) The total number of fluorine atoms contained in one chain is preferably in the range of 18 to 200, more preferably in the range of 25 to 150.

  The active energy ray-curable group possessed by the fluorine-containing polymerizable resin (C) used in the present invention is an ethylenic double bond that exhibits curability when irradiated with active energy rays. Specifically, the structural formula U- The thing shown by 1-U-3 is mentioned.

  In order to introduce the above active energy ray-curable group into the fluorine-containing polymerizable resin (C) used in the present invention, after obtaining the polymer (P1) or the polymer (P2), the side chain of the polymer A compound (c3) having a functional group (R2) reactive to the reactive functional group (R1) and an active energy ray-curable group is reacted with the reactive functional group (R1) present in 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 a reactive functional group. A polymer (P1) obtained by copolymerizing a polymerizable unsaturated monomer (c2) having a group (R1) as an essential monomer component is reactive with the functional group (R1). What is obtained by reacting the compound (c3) having the functional group (R2) and the active energy ray-curable group (hereinafter, abbreviated as “fluorinated polymerizable resin (C1)”) or reaction. A polymer (P2) of a polymerizable unsaturated monomer (B) having a reactive functional group (R1), a poly (perfluoroalkylene ether) chain, and the reactive functional group (R1) at both ends thereof Has a reactive functional group (R2) What is obtained by reacting a compound (c1 ′) with a compound (c3) having a functional group (R2) reactive to the functional group (R1) and an active energy ray-curable group (hereinafter referred to as “the functional group (R1)”) This is preferably abbreviated as “fluorinated polymerizable resin (C2)”) because it is easy to produce industrially.

  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'-5 at the both terminal of a poly (perfluoroalkylene ether) chain | strand is mentioned, for example.

  Among these 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. Moreover, since chemical resistance improves, the methacryloyloxy group represented by Structural formula U'-2 and the styryl methoxy group represented by Structural formula U'-5 are preferable.

  Examples of the compound (c1) having the acryloyloxy group described above include those represented by the following structural formulas (c1-1) to (c1-13). In the following structural formulas, “—PFPE—” represents a poly (perfluoroalkylene ether) chain.

  Among these, the structural formulas (c1-1) and (c1) are particularly easy because the industrial production of the compound (c1) itself is easy and the polymerization reaction when producing the polymer (P1) is also easy. -2), (c1-5) and (c1-6) are preferred. Moreover, since chemical resistance improves, the said structural formula (c1-2), (c1-4), (c1-12), (c1-13) is preferable.

  As a method for producing the compound (c1), for example, (meth) acrylic acid chloride or chloromethylstyrene is dehydrochlorinated with respect to a compound having one hydroxyl group at each end of a poly (perfluoroalkylene ether) chain. A method obtained by reaction, 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 methacrylate, Of poly (perfluoroalkylene ether) chain Relative to the compound having the end one isocyanate group, and a method of reacting a 2-hydroxyethyl acrylamide. Among these, a method obtained by dehydrochlorinating (meth) acrylic acid chloride or chloromethylstyrene with respect to a compound having one hydroxyl group at both ends of a poly (perfluoroalkylene ether) chain; A method obtained by subjecting (meth) acryloyloxyethyl isocyanate to a urethanization reaction is particularly preferable in terms of easy reaction in production.

  Here, the method for producing the polymer (P1) includes the compound (c1), a polymerizable unsaturated monomer (c2) having a reactive functional group (R1), and, if necessary, other polymerizable groups. A method of polymerizing a saturated monomer in an organic solvent using a polymerization initiator can be mentioned. 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 polymer (P1) obtained by the above method preferably has a number average molecular weight in the range of 800 to 3,000 as measured by GPC, and more preferably in the range of 1,000 to 2,000. The polymer (P1) preferably has a weight average molecular weight in the range of 1,500 to 50,000, more preferably in the range of 2,000 to 25,000. If the average molecular weight of the polymer (P1) is within these ranges, it is possible to prevent the occurrence of crosslinking insolubilization during the polymerization. Further, the number of polymerizable unsaturated groups in one molecule of the finally obtained fluorine-containing polymerizable resin (C1) can be increased.

  The polymer (P1) thus obtained is reacted with a compound (c3) containing a functional group (R2) reactive to the functional group (R1) and an active energy ray-curable group. Thus, the desired fluorine-containing polymerizable resin (C1) is obtained.

  Here, examples of the functional group (R2) of the compound (c3) include a hydroxyl group, an isocyanate group, an epoxy group, and a carboxyl group. For example, when the reactive functional group (R1) is a hydroxyl group, the functional group (R2) includes an isocyanate group. When the reactive functional group (R1) is an isocyanate group, the functional group (R2) When the reactive functional group (R1) is an epoxy group, a carboxyl group is exemplified as the functional group (R2), and when the reactive functional group (R1) is a carboxyl group, the functional group is functional. An epoxy group is mentioned as group (R2).

  As such a compound (c3), the thing similar to what was illustrated as said polymerizable unsaturated monomer (c2) can be used. In addition, 2-hydroxy-3-acryloyloxypropyl methacrylate, pentaerythritol triacrylate, and dipentaerythritol pentaacrylate can be used as those having two or more active energy ray-curable groups.

  Of these, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, 4-hydroxybutyl acrylate are particularly preferred because of their polymerization curability upon irradiation with active energy rays such as ultraviolet rays. 1,4-cyclohexanedimethanol monoacrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, N- (2-hydroxyethyl) acrylamide, 2-acryloyloxyethyl isocyanate, 4-hydroxybutyl acrylate glycidyl ether and acrylic acid are preferred.

  A method of reacting the polymer (P1) with a compound (c3) containing a functional group (R2) reactive to the functional group (R1) and an active energy ray-curable group is a compound (c3). ) In which the active energy ray-curable group is not polymerized. For example, the reaction is preferably carried out by adjusting the temperature condition in the range of 30 to 120 ° C. This reaction is preferably carried out in the presence of a catalyst or a polymerization inhibitor, and if necessary in the presence of an organic solvent.

  For example, when the functional group (R1) is a hydroxyl group and the functional group (R2) is an isocyanate group, or when the functional group (R1) is an isocyanate group and the functional group (R2) is a hydroxyl group, P-methoxyphenol, hydroquinone, 2,6-di-t-butyl-4-methylphenol, etc. are used as polymerization inhibitors, and dibutyltin dilaurate, dibutyltin diacetate, tin octylate, octylic acid as urethanization reaction catalysts A method of reacting at a reaction temperature of 40 to 120 ° C., particularly 60 to 90 ° C. using zinc or the like is preferable. When the functional group (R1) is an epoxy group and the functional group (R2) is a carboxyl group, or the functional group (R1) is a carboxyl group and the functional group (R2) 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, tetramethyl chloride. Using quaternary ammoniums such as ammonium, tertiary phosphines such as triphenylphosphine, and quaternary phosphoniums such as tetrabutylphosphonium chloride, the reaction is carried out at a reaction temperature of 80 to 130 ° C., particularly 100 to 120 ° C. It is preferable to make it.

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

  Next, in order to produce the fluorine-containing polymerizable resin (C2), first, a polymerizable unsaturated monomer (c2) having a reactive functional group (R1) 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 includes a polymerizable unsaturated monomer (c2) having a reactive functional group (R1) and, if necessary, other polymerizable unsaturated monomers. The method of superposing | polymerizing using a polymerization initiator 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 preferably has a number average molecular weight in the range of 800 to 3,000 as measured by GPC, and preferably in the range of 1,000 to 2,000. The polymer (P2) preferably has a weight average molecular weight in the range of 1,200 to 6,000, and preferably in the range of 1,500 to 5,000. When the average molecular weight of the polymer (P2) is within these ranges, it is possible to prevent the occurrence of crosslinking insolubilization during the polymerization.

  Next, a compound (c1) having a poly (perfluoroalkylene ether) chain and a functional group (R2) having reactivity to the reactive functional group (R1) at both ends of the obtained polymer (P2). ′) And a compound (c3) containing a functional group (R2) having reactivity with the functional group (R1) and an active energy ray-curable group, to produce a desired fluorine-containing polymerization. Resin (C2) is obtained.

  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 amount of the reactive functional group (R1) in the polymer (P2) and the reaction ratio of the compound (c1 ′) and the compound (c3) to the reactive functional group (R1) can be adjusted appropriately. It is desirable from the point that the effect of the present invention is remarkable. Specifically, the amount of the reactive functional group (R1) in the polymer (P2) is 100 to 200 g / eq. The functional group concentration is preferably in the range of from the viewpoint that the antifouling property and scratch resistance become better, and in the compound (c1 ′) with respect to 1 mol of the reactive functional group (R1). The functional group (R2) is in a ratio such that the functional group (R2) is 0.05 to 0.20 mol and has reactivity in the compound (c3) with respect to 1 mol of the reactive functional group (R1). Is preferably reacted at a ratio of 0.80 to 0.95 mol.

  Here, the functional group (R2) in the compound (c1 ′) having a poly (perfluoroalkylene ether) chain and a functional group (R2) having reactivity to the reactive functional group (R1) at both ends thereof is , Hydroxyl group, isocyanate group, epoxy group, carboxyl group and the like. For example, when the reactive functional group (R1) is a hydroxyl group, the functional group (R2) includes an isocyanate group. When the reactive functional group (R1) is an isocyanate group, the functional group (R2) When the reactive functional group (R1) is an epoxy group, a carboxyl group is exemplified as the functional group (R2), and when the reactive functional group (R1) is a carboxyl group, the functional group is functional. An epoxy group is mentioned as group (R2).

  Examples of such a compound (c1 ′) include compounds represented by the following structural formulas c1′-1 to c1′-6, and polyfunctional isocyanates such as hexamethylene diisocyanate and tolylene diisocyanate. Examples thereof include compounds and compounds modified with bifunctional epoxy resins such as bisphenol type epoxy resins. In the following structural formulas, “—PFPE—” represents a poly (perfluoroalkylene ether) chain. Among these, the compounds represented by the following structural formulas c1′-1 to c1′-6 that are not modified are preferable. Particularly, when the functional group (R1) is an isocyanate group, the following structural formula (c1′- The compound (c1 ′) represented by 1) is preferable from the viewpoint of excellent reactivity with respect to the functional group (R1).

  Moreover, the compound (d3) used here can use the same thing as the compound (d3) used in the case of manufacture of above-mentioned fluorine-containing polymeric resin (C1).

  As described above, the reaction between the polymer (P2), the compound (d1 ′) and the compound (d3) is performed by reacting the polymer (P2) with the compound (d1 ′) and then reacting the compound (d3). Alternatively, after the polymer (P2) and the compound (d3) are reacted, the compound (d1 ′) may be reacted, or the compound (d1 ′) and the compound (d3) 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 functional group (R1) in the polymer (P2) and the functional group (R2) in the compound (d1 ′) is a hydroxyl group and the other is an isocyanate group, or the polymer (P2) When one of the functional group (R1) in the compound and the functional group (R2) in the compound (d3) is a hydroxyl group and the other is an isocyanate group, p-methoxyphenol, hydroquinone, 2,6- Di-t-butyl-4-methylphenol or the like is used, dibutyltin dilaurate, dibutyltin diacetate, tin octylate, zinc octylate or the like is used as the urethanization reaction catalyst, and the reaction temperature is 40 to 120 ° C, particularly 60 to A method of reacting at 90 ° C. is preferred.

  In addition, when one of the functional group (R1) in the polymer (P2) and the functional group (R2) in the compound (d1 ′) is a carboxyl group and the other is an epoxy group, or the polymer (P2 ) And the functional group (R2) in the compound (d3) are carboxyl groups and the other is an epoxy group, p-methoxyphenol, hydroquinone, 2, 6-di-t-butyl-4-methylphenol or the like, tertiary amines such as triethylamine as the esterification reaction catalyst, quaternary ammoniums such as tetramethylammonium chloride, tertiary such as triphenylphosphine Use phosphines, quaternary phosphoniums such as tetrabutylphosphonium chloride, etc., and react at a reaction temperature of 80 to 130 ° C., particularly 100 to 120 ° C. Preferred.

  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 (C1) or the fluorine-containing polymerizable resin (C2) has a number average molecular weight (Mn) of 1,000 to 10,000. And the weight average molecular weight (Mw) is preferably in the range of 2,000 to 150,000, the number average molecular weight (Mn) is in the range of 1,500 to 5,000, and the weight. The average molecular weight (Mw) is more preferably in the range of 4,000 to 100,000. Those having an average molecular weight in the range are preferable from the viewpoint that a highly crosslinked and excellent developability can be obtained without causing gelation during the production of the fluorine-containing polymerizable resin (C).

  Here, the number average molecular weight (Mn) and the weight average molecular weight (Mw) are values converted to polystyrene based on gel permeation chromatography (hereinafter abbreviated as “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 (THF)
Flow rate 1.0 ml / min Sample: 1.0 mass% tetrahydrofuran solution filtered in terms of resin solids with a microfilter (5 μl).
Standard sample: The following monodisperse polystyrene having a known molecular weight was used in accordance with the measurement manual of “GPC-8020 model II version 4.10”.

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

  Further, the fluorine atom content in the fluorine-containing polymerizable resin (C) is more compatible with other components such as a polymerizable monomer (D) and a polymerizable resin (E) described later, Since high antifouling property and abrasion resistance are obtained, what is 5-40 mass% is preferable, what is 10-35 mass% is more preferable, and what is 18-30 mass% is still more preferable.

  Furthermore, the content of the active energy ray-curable group in the fluorine-containing polymerizable resin (C) is such that the active energy ray-curable group equivalent is 250 to 500 g / eq. It is preferable from the point which is excellent in the antifouling property of a cured coating film, and especially 300-400 g / eq. It is particularly preferable that the range is

  The compounding amount of the fluorine-containing polymerizable resin (C) in the active energy ray-curable composition of the present invention is 100 parts by mass of the nonvolatile content in the active energy ray-curable composition (the alkoxysilane condensate and the polymerization initiator). It is preferable that it is 0.01-10 mass parts with respect to. 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.

  Moreover, as for the compounding ratio (mass ratio) of the said alkoxysilane condensate and the said fluorine-containing polymeric resin (C), the former 30-95: The latter 70-5 are preferable, The former 50-90: The latter 50-10 are more. 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 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 polymerizable group such as a (meth) acryl group, a polymerizable monomer (D) having a polymerizable group such as a (meth) acryl group, polymerization 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, a cation such as a vinyl ether group, an epoxy group, or an oxetanyl group is used. It is preferable to use a polymerizable monomer (D) having a polymerizable group and a polymerizable resin (E).

  Among the polymerizable monomers (D), examples of the monofunctional monomer having a polymerizable group include N-vinylcaprolactam, N-vinylpyrrolidone, N-vinylcarbazole, vinylpyridine, acrylamide, N, N-dimethyl (meta ) Acrylamide, isobutoxymethyl (meth) acrylamide, t-octyl (meth) acrylamide, diacetone (meth) acrylamide, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, 7-amino-3,7-dimethyloctyl (Meth) acrylate, acryloylmorpholine, lauryl (meth) acrylate, dicyclopentadienyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentenyl (meth) acrylate 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 polymerizable group include trimethylolpropane tri (meth) acrylate, triethylene oxide-modified trimethylolpropane tri (meth) acrylate, and tripropylene oxide-modified glycerol tris. (Meth) acrylate, triethylene oxide modified glycerin tri (meth) acrylate, triepichlorohydrin modified glycerin 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, ditri Tyrolpropane 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, di Examples include pentaerythritol 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 polymerizable group include epoxy (meth) acrylates, aliphatic polyisocyanates or aromatic polyisocyanates obtained by reacting a compound having a plurality of epoxy groups with (meth) acrylic acid. And urethane (meth) acrylate obtained by reacting (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, bis (2- Mono- or di (meth) acrylates of trivalent alcohols such as (meth) acryloyloxyethyl) hydroxyethyl isocyanurate, or mono- and di (meta) 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 obtained by modifying the hydroxyl group of this compound with ε-caprolactone; dipropylene glycol mono (meth) acrylate, diethylene glycol mono (meth) acrylate, polypropylene glycol mono ( A) (meth) acrylate compounds having an oxyalkylene chain such as acrylate and polyethylene glycol mono (meth) acrylate; blocks such as polyethylene glycol-polypropylene glycol mono (meth) acrylate and polyoxybutylene-polyoxypropylene mono (meth) acrylate (Meth) acrylate compound having an oxyalkylene chain having a structure; poly (ethylene glycol-tetramethylene glycol) mono (meth) acrylate, poly (propylene glycol-tetramethylene glycol) mono (meth) acrylate, or other random structure oxyalkylene chain (Meth) acrylate compounds having

  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 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 ray, a photopolymerization initiator (F) is added to the active energy ray-curable composition. If necessary, a photosensitizer is further added. On the other hand, when ionizing radiation such as electron beam, α-ray, β-ray, and γ-ray is used, it cures quickly without using a photopolymerization initiator or photosensitizer. There is no.

  When the active energy ray polymerizable group of each component contained in the active energy ray curable composition of the present invention is a polymerizable group, the photopolymerization initiator (F) includes an intramolecular cleavage type photopolymerization initiator and Examples include 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 composition of the present invention is a cationic polymerizable group, for example, triallylsulfonium- Examples include hexafluorophosphate salts, phosphorus aromatic sulfonium-hexafluorophosphate salts, phosphorus aromatic sulfonium-hexafluoroantimony salts, diallyl iodonium salts, 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.

  The amount of these photopolymerization initiators and photosensitizers used is preferably 0.01 to 20 parts by weight, more preferably 0.3 parts per 100 parts by weight of the non-volatile component in the active energy ray-curable composition. -10 parts by mass.

  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. As various compounding materials for the purpose of adjusting coating properties and coating film properties, for example, various organic solvents, acrylic resins, phenol resins, polyester resins, urethane resins, urea resins, melamine resins, alkyd resins, epoxy resins, polyamide resins Various resins such as polycarbonate resin, petroleum resin, fluororesin, PTFE (polytetrafluoroethylene), polyethylene, carbon, titanium oxide, alumina, copper, silica fine particles, etc., polymerization initiator, polymerization prohibition Agent, antistatic agent, antifoaming agent, viscosity modifier, light stabilizer, weathering stabilizer, heat stabilizer, antioxidant, rust inhibitor, Lip 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.

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

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

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

  Examples of the substrate on which the active energy ray-curable composition of the present invention is applied include a plastic substrate; a ceramic substrate such as glass; 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 composition of the present invention can be used as long as it is a normal molded product, but a film or sheet is preferred.

  The application method of the active energy ray-curable coating composition of the present invention varies depending on the application. For example, gravure coater, roll coater, comma coater, knife coater, air knife coater, curtain coater, kiss coater, shower coater, wheeler coater, spin Examples thereof include a coating method using a coater, dipping, screen printing, spray, applicator, bar coater, etc., or a molding method using various molds.

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

  As an article which can impart antifouling properties (ink repellency, fingerprint resistance, etc.) using the active energy ray-curable coating composition of the present invention, a film for polarizing plate of a liquid crystal display (LCD) such as a TAC film; Various display screens such as plasma display (PDP) and organic EL display; touch panel; housing or screen of electronic terminal such as mobile phone; transparent protective film for liquid crystal display color filter (hereinafter referred to as “CF”); liquid crystal TFT Organic insulating film for arrays; inkjet ink for forming electronic circuits; optical recording media such as CD, DVD, Blu-ray disc; transfer film for insert mold (IMD, IMF); rubber roller for OA equipment such as copiers and printers; , The glass surface of the reading part of OA equipment such as a scanner; Optical lenses such as money; Windshields for watches such as watches; Glass surfaces; Windows for various vehicles such as automobiles and railway vehicles; Cover glass or film for solar cells; Various building materials such as decorative panels; Window glass for houses; Examples include woodworking materials, artificial and synthetic leather, various plastic molded products such as housings for home appliances, and FRP bathtubs. By applying the active energy ray-curable coating composition of the present invention to the surface of these articles and irradiating active energy rays such as ultraviolet rays to form a cured coating film, antifouling properties can be imparted to the article surfaces. it can. Moreover, it is also possible to add antifouling property to the article surface by adding the alkoxysilane condensate of the present invention to various paints suitable for each article, coating and drying.

  In addition, as a coating material that can add the alkoxysilane condensate of the present invention and impart antifouling properties (ink repellency, fingerprint resistance, etc.) to the coating film, a hard coat of a polarizing plate film for LCD such as a TAC film Materials, anti-glare (AG: anti-glare) coating material or anti-reflection (LR) coating material; hard coating materials for various display screens such as plasma display (PDP), organic EL display; hard coating materials for touch panel; liquid crystal display, organic EL Color resist, printing ink, ink-jet ink or paint for forming each pixel of RGB used for CF used in imaging devices such as displays, CCDs, CMOSs, etc .; Black resist for CF black matrix, printing ink, Inkjet ink or paint; plasma display (PDP) Resin composition for pixel partition walls of organic EL displays, etc .; Paint or hard coat material for casings of electronic terminals such as mobile phones; Hard coat material for screens of electronic terminals such as mobile phones; For transparent protective films that protect the CF surface Paint: Organic insulating film paint for liquid crystal TFT array; inkjet ink for forming electronic circuit; hard coat material for optical recording media such as CD, DVD, Blu-ray disc; hard coat material for transfer film for insert mold (IMD, IMF); Coating material for rubber rollers for OA equipment such as copiers and printers; Glass coating material for reading parts of OA equipment such as copying machines and scanners; Coating material for optical lenses such as cameras, video cameras and glasses; Watches such as watches Windshields, glass coating materials; window coating materials for various vehicles such as automobiles and railway vehicles; solar cell coating materials -Glass or film anti-reflective coatings; printing inks or paints for various building materials such as decorative panels; residential window glass coatings; furniture and other woodwork coatings; artificial and synthetic leather coatings; And various plastic molded article paints or coating materials; FRP bathtub paints or coating materials.

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

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

  In addition, when the active energy ray-curable coating composition of the present invention is used for an antiglare coating material for a protective film of a polarizing plate for LCD, after the coating material is contacted with a mold having an uneven surface shape before curing, 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 coating layer is embossed to impart antiglare properties.

  Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. The molecular weight of the synthesized fluorine-containing polymerizable resin and the like was measured under the following conditions.

[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 (THF)
Flow rate 1.0 ml / min Sample: 1.0 mass% tetrahydrofuran solution filtered in terms of resin solids with a microfilter (5 μl).
Standard sample: The following monodisperse polystyrene having a known molecular weight was used in accordance with the measurement manual of “GPC-8020 model II version 4.10”.

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

(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)
Perfluoropoly having a hydroxyl group at both ends of 25 to 80 fluorine atoms represented by the following structural formula (c1′-1-1) in a glass flask equipped with a stirrer, thermometer, condenser, and dropping device 20 parts by mass of an ether compound, 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 were added, and stirring was started under an air stream. Then, while maintaining the inside of the flask 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 abbreviated as “MIBK”) as a solvent was charged in another glass flask equipped with a stirrer, a thermometer, a condenser, and a dropping device, and stirred 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 dropping, the mixture was stirred at 105 ° C. for 10 hours, and then the solvent was distilled off under reduced pressure to obtain 63.7 parts by mass of the polymer (P1-1).

  Next, 107.6 parts by mass of methyl ethyl ketone (hereinafter abbreviated as “MEK”) as a solvent, 0.04 parts by mass of p-methoxyphenol as a polymerization inhibitor, 0.3 parts by mass of dibutylhydroxytoluene as an antioxidant, urethane 0.03 part by mass of tin octylate was charged as a catalyst, and 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, and then reacted by raising the temperature to 80 ° C. and stirring for 10 hours. As a result, disappearance of the isocyanate group was confirmed by IR spectrum measurement, and the fluorine-containing polymerizable resin ( An MEK solution containing 50% by mass of C-1) was obtained. As a result of measuring the molecular weight of the obtained fluorinated polymerizable resin by GPC (polystyrene equivalent molecular weight), it was a number average molecular weight of 2,400 and a weight average molecular weight of 7,100.

Example 1
In a glass flask equipped with a stirrer, a condenser tube, and a thermometer, 0.89 parts by mass of alkoxysilane (A-1) having a polydimethylsiloxane chain obtained in Synthesis Example 1, 100 parts by mass of MEK, and dibutyl as a polymerization inhibitor 0.1 part by mass of hydroxytoluene, 0.01 part by mass of p-methoxyphenol as a polymerization inhibitor, 0.95 part by mass of water, and phosphoric acid-modified product (“A-3” manufactured by Sakai Chemical Industry Co., Ltd.) 1 part by mass was charged, heated to 70 ° C. and stirred for 1.5 hours. Next, 8.75 parts by mass of 3-acryloxypropyltrimethoxysilane was added and reacted at 70 ° C. for 4.5 hours. After completion of the reaction, a part of the solvent was distilled off under air blowing to obtain a MEK solution containing 10% by mass of the alkoxysilane condensate (1). As a result of measuring the molecular weight of this alkoxysilane condensate (1) by GPC (polystyrene equivalent molecular weight), it was a number average molecular weight 2,700 and a weight average molecular weight 4,600. In addition, the GPC chart of this alkoxysilane condensate (1) is shown in FIG.

(Preparation of active energy ray-curable composition)
Using the alkoxysilane condensate (1) obtained in Example 1 and the fluorine-containing polymerizable resin (C-1) obtained in Synthesis Example 2, an active energy ray-curable composition is prepared as follows. did.

(Example 2)
47.5 parts by mass of pentafunctional non-yellowing urethane acrylate (hereinafter abbreviated as “polyfunctional urethane acrylate”), 47.5 parts by mass of dipentaerythritol hexaacrylate (hereinafter abbreviated as “DPHA”), light In Example 1, after mixing and dissolving 5 mass parts of polymerization initiators ("Irgacure 184" manufactured by Ciba Specialty Chemicals Co., Ltd., 1-hydroxycyclohexyl phenyl ketone), 25 mass parts of butyl acetate, and 80 mass parts of MEK. 50 parts by mass of a 10% by mass MEK solution of the obtained alkoxysilane condensate (1) (5 parts by mass as an alkoxysilane condensate) was added and mixed uniformly to obtain an active energy ray-curable composition (1). It was.

(Example 3)
48.9 parts by mass of polyfunctional urethane acrylate, 48.9 parts by mass of DPHA, 5 parts by mass of photopolymerization initiator (“Irgacure 184”, 1-hydroxycyclohexyl phenyl ketone, manufactured by Ciba Specialty Chemicals Co., Ltd.), 25 parts by mass of butyl acetate And after mixing and dissolving 113.2 parts by mass of MEK, 12 parts by mass of a 10% by mass MEK solution of the alkoxysilane condensate (1) obtained in Example 1 (1.2 parts by mass as the alkoxysilane condensate) Then, 2 parts by mass of a 50% by mass MEK solution of the fluorinated polymerizable resin (C-1) obtained in Synthesis Example 2 (1 part by mass as the fluorinated polymerizable resin) was further added. It mixed uniformly and the active energy ray hardening-type composition (2) was obtained.

Example 4
47 parts by mass of polyfunctional urethane acrylate, 47 parts by mass of DPHA, 5 parts by mass of photopolymerization initiator (“Irgacure 184”, 1-hydroxycyclohexyl phenyl ketone, manufactured by Ciba Specialty Chemicals Co., Ltd.), 25 parts by mass of butyl acetate, and MEK79 After mixing and dissolving parts by mass, 50 parts by mass of a 10% by mass MEK solution of the alkoxysilane condensate (1) obtained in Example 1 (5 parts by mass as alkoxysilane condensate) was added and mixed uniformly. Further, 2 parts by mass of a 50% by mass MEK solution of the fluoropolymer resin (C-1) obtained in Synthesis Example 2 (1 part by mass as a fluoropolymer resin) was added and mixed uniformly to obtain active energy. A linear curable composition (3) was obtained.

(Comparative Example 1)
50 parts by mass of polyfunctional urethane acrylate, 50 parts by mass of DPHA, 5 parts by mass of photopolymerization initiator (“Irgacure 184”, 1-hydroxycyclohexyl phenyl ketone, manufactured by Ciba Specialty Chemicals Co., Ltd.), 25 parts by mass of butyl acetate, and MEK125 Mass parts were mixed and dissolved uniformly to obtain an active energy ray-curable composition (4).

(Comparative Example 2)
49.5 parts by mass of polyfunctional urethane acrylate, 49.5 parts by mass of DPHA, 5 parts by mass of photopolymerization initiator (“Irgacure 184”, 1-hydroxycyclohexyl phenyl ketone, manufactured by Ciba Specialty Chemicals Co., Ltd.), 25 parts by mass of butyl acetate After mixing and dissolving 124 parts by mass of MEK, 2 parts by mass of a 50% by mass MEK solution of the fluoropolymer resin (C-1) obtained in Synthesis Example 2 (1 part by mass as the fluoropolymer resin) Was added and mixed uniformly to obtain an active energy ray-curable composition (5).

  Table 1 shows the compositions of the active energy ray-curable compositions obtained in Examples 2 to 4 and Comparative Examples 1 and 2.

[Evaluation of active energy ray-curable composition]
As described below, a coating film was prepared as an evaluation sample, and the antifouling property was evaluated.

(Example 5)
The active energy ray-curable composition (1) obtained in Example 2 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 3 kJ / m ² ) to prepare a coated film.

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 stain adhesion prevention property was evaluated according to the following criteria.
A: The number of repetitions is 10 times or more.
B: The number of repetitions is 5 times or more and less than 10 times.
C: The number of repetitions is 1 or more and less than 5 times.
D: The number of repetitions is 0.

(Example 6)
The same procedure as in Example 5 was performed except that the active energy ray-curable composition (2) obtained in Example 3 was used instead of the active energy ray-curable composition (1) used in Example 5. Then, a coated film was prepared and the antifouling property was evaluated.

(Example 7)
The same procedure as in Example 5 was performed except that the active energy ray-curable composition (3) obtained in Example 4 was used instead of the active energy ray-curable composition (1) used in Example 5. Then, a coated film was prepared and the antifouling property was evaluated.

(Example 8)
Instead of the active energy ray-curable composition (1) used in Example 5, the active energy ray-curable composition (3) obtained in Example 4 was used, and the curing conditions were changed from a nitrogen atmosphere to an air atmosphere. Except having changed, it carried out similarly to Example 5, produced the coating film, and evaluated dirt adhesion prevention property.

(Comparative Example 3)
The same procedure as in Example 5 was performed except that the active energy ray-curable composition (4) obtained in Comparative Example 1 was used in place of the active energy ray-curable composition (1) used in Example 5. Then, a coated film was prepared and the antifouling property was evaluated.

(Comparative Example 4)
The same procedure as in Example 5 was performed except that the active energy ray-curable composition (5) obtained in Comparative Example 2 was used in place of the active energy ray-curable composition (1) used in Example 5. Then, a coated film was prepared and the antifouling property was evaluated.

(Comparative Example 5)
Instead of the active energy ray-curable composition (1) used in Example 5, the active energy ray-curable composition (4) obtained in Comparative Example 1 was used, and the curing conditions were changed from a nitrogen atmosphere to an air atmosphere. Except having changed, it carried out similarly to Example 5, produced the coating film, and evaluated dirt adhesion prevention property.

(Comparative Example 6)
Instead of the active energy ray-curable composition (1) used in Example 5, the active energy ray-curable composition (5) obtained in Comparative Example 2 was used, and the curing conditions were changed from a nitrogen atmosphere to an air atmosphere. Except having changed, it carried out similarly to Example 5, produced the coating film, and evaluated dirt adhesion prevention property.

  The evaluation results in Examples 5 to 8 and Comparative Examples 3 to 6 are shown in Table 2.

  From the evaluation results shown in Table 2, it was found that Example 5 using the active energy ray-curable composition (1) in which the alkoxysilane condensate of the present invention was blended had good antifouling properties.

  In addition to the alkoxysilane condensate of the present invention, an active energy ray-curable composition (2) or (3) containing a poly (perfluoroalkylene ether) chain and a fluorine-containing polymerizable resin having an active energy ray polymerizable group The used Example 6 or 7 was found to have a very good antifouling property.

  Example 8 is an example in which the same active energy ray-curable composition (3) as that in Example 7 was used and cured by irradiation with active energy rays in an air atmosphere (in the presence of oxygen). Normally, in an air atmosphere, curing tends to be insufficient due to oxygen inhibition and the dirt adhesion preventing property tends to decrease. In Example 8, however, very excellent dirt almost equivalent to curing in a nitrogen atmosphere was obtained. It was found to have anti-adhesive properties.

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

  Although the comparative example 3 is an example using the active energy ray hardening-type composition (4) which did not mix | blend the alkoxysilane condensate of this invention, it turned out that dirt adhesion prevention property is inadequate.

  Comparative Example 4 is an example using an active energy ray-curable composition (5) containing only a fluorine-containing polymerizable resin having a poly (perfluoroalkylene ether) chain and an active energy ray polymerizable group. The anti-smudge property was improved as compared with Comparative Example 3, but sufficient anti-smudge property was not obtained.

  Comparative Example 5 is an example in which the active energy ray-curable composition (4) used in Comparative Example 3 was used for irradiation and curing in an air atmosphere, but it was cured in a nitrogen atmosphere. As in Comparative Example 3, it was found that the antifouling property was insufficient.

  Comparative Example 6 is an example in which the active energy ray-curable composition (5) used in Comparative Example 4 was cured by irradiation with an active energy ray in an air atmosphere, but was cured in a nitrogen atmosphere. It was found from Comparative Example 4 that the antifouling property was lowered.

Claims (7)

  An alkoxysilane condensate obtained by condensing an alkoxysilane (A) having a polyalkylsiloxane chain or a polyarylsiloxane chain and an alkoxysilane (B) having an active energy ray polymerizable group.   The alkoxysilane condensate 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 alkoxysilane condensate according to claim 2, wherein the polydimethylsiloxane chain has a molecular weight of 1,000 to 10,000.   An active energy ray-curable composition comprising the alkoxysilane condensate according to any one of claims 1 to 3.   The active energy ray-curable composition according to claim 4, further comprising a fluorine-containing polymerizable resin (C) having a poly (perfluoroalkylene ether) chain and an active energy ray polymerizable group.   A cured product obtained by curing the active energy ray-curable composition according to claim 4 or 5.   An article comprising a coating film obtained by curing the active energy ray-curable composition according to claim 4 or 5.

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