Polymerizable surface modifier for water-dispersible coating compositions, water-dispersible coating compositions containing the polymerizable surface modifier, and coated articles.

Abstract

To provide a polymerizable surface control agent to be added to a water-dispersible coating composition, which, by addition to the water-dispersible coating composition, can make the composition exhibit an excellent defoaming property or smoothness and does not degrade characteristics of a cured film such as an antifogging property, antistaticity, adhesion, a hard coat property, and the like, the coating film being obtained by curing the coating composition with heat or active energy rays.SOLUTION: Provided is a polymerizable surface control agent for a water-dispersible coating composition, comprising a polymerizable polyoxyalkylene compound (A) represented by general formula (I) and hydrophobic silica (B): R1(-OA)n-OR2 (I) (in the formula, R1 represents a group having a (meth)acryloyl group; R2 represents an alkyl group, an alkenyl group, or an acyl group; OA represents an oxyalkylene group; and n represents an integer of 2-50 and, when n is 2 or larger, two or more A's may be the same or different and, when OA is an oxyethylene group, n is 0-10).SELECTED DRAWING: None

Description

[Technical Field] 【0001】 The present invention relates to a polymerizable surface modifier for water-dispersible coating compositions, a water-dispersible coating composition containing the polymerizable surface modifier, and a coated article. 【0002】 A polymer solution comprising a (meth)acrylate monomer and a high-boiling point alcohol has been disclosed as a leveling agent added to a two-component polyurethane or epoxy paint to improve its fluidity (Patent Document 1). Furthermore, an antifoaming agent containing a non-volatile component is disclosed as a surface modifier for active energy ray curable film-forming compositions, which contains a copolymer having an addition copolymerized main chain and a side chain having at least one unsaturated group, such as a (meth)acryloyl group and an alkenyl group (Patent Document 2). Furthermore, polyether-modified silicone oil, polyester-modified silicone oil, and perfluoro-modified silicone oil have been disclosed as leveling agents contained in hard coat resin compositions (Patent Document 3). Furthermore, an antifoaming agent containing hydrocarbon oil, hydrophobic silica, polyoxyalkylene compound, and polyhydric alcohol fatty acid ester has been disclosed (Patent Document 4). [Prior art documents] [Patent Documents] 【0003】 [Patent Document 1] Special Publication No. 04-40391 [Patent Document 2] Patent No. 5450922 [Patent Document 3] Japanese Patent Publication No. 2006-63244 [Patent Document 4] WO2016 / 140078 publication [Overview of the project] [Problems that the invention aims to solve] 【0004】 However, even though conventional surface modifiers such as leveling agents and defoaming agents are excellent in leveling properties and defoaming properties, the polymer solution, which is the main component, is hydrophobic and contains an organic solvent, so it may be difficult to disperse and dissolve it in a water-dispersible coating composition. In addition, in the cured coating film using it, as seen in the remaining water marks in the anti-fogging property evaluation, the surface modifier itself bleeds out and is oriented toward the substrate side, so the adhesion of the coating film is impaired. Furthermore, in the cured coating film of a composition having a modified silicone oil, the silicone oil is oriented on the outermost surface, so properties such as anti-fogging property and antistatic property may be lost. Therefore, there is a demand for a surface modifier that can function more multifunctionally while maintaining the properties of the surface modifier itself. An object of the present invention is to provide a polymerizable surface modifier to be added to a water-dispersible coating composition, which can exhibit excellent defoaming properties (foam-breaking and foam-suppressing effects) or smoothness when added to the water-dispersible coating composition, and does not deteriorate properties such as anti-fogging property, antistatic property, adhesion, and hard coat property in the cured coating film obtained by irradiating it with heat or active energy rays. 【Means for Solving the Problems】 【0005】 This application includes the following inventions. (1) A polymerizable surface modifier for a water-dispersible coating composition containing a polymerizable polyoxyalkylene compound (A) represented by the general formula (I) and hydrophobic silica (B). R 1 (-OA) n -OR 2 (I) [In the formula, R 1 represents a group having a (meth)acryloyl group. R 2 represents an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, or an acyl group having 2 to 30 carbon atoms. OA represents an oxyalkylene group having 2 to 4 carbon atoms. n represents an integer of any one of 2 to 50. When n is 2 or more, two or more As may be the same or different. However, when OA is an oxyethylene group, n is 0 to 10. (2) The above-mentioned polymerizable surface conditioner, wherein the polymerizable polyoxyalkylene compound (A) contains one or more selected from the group consisting of polymerizable polyoxyalkylene alkyl ethers (A-1) and polyoxyalkylene (meth) acrylates (A-2). (3) The above-mentioned polymerizable surface conditioner, wherein the polymerizable polyoxyalkylene alkyl ether (A-1) is a compound represented by the formula (I-1), and the polyoxyalkylene (meth) acrylate (A-2) is a compound represented by the formula (I-2). R 11 (-OA) n -OR 2 (I-1) R 12 (-OA) n -OR 2 (I-2) [In the formula, R 11 represents a group having a (meth) acryloyl group in part. R 12 represents a (meth) acryloyl group. R 2 represents an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, or an acyl group having 2 to 30 carbon atoms. OA represents an oxyalkylene group having 2 to 4 carbon atoms. n represents an integer of any one of 2 to 50. When n is 2 or more, two or more As may be the same or different. However, when OA is an oxyethylene group, n is 0 to 10. (4) The above-mentioned polymerizable surface conditioner, wherein the polymerizable polyoxyalkylene compound (A) contains two or more different compounds. (5) The above-mentioned polymerizable surface conditioner, wherein the polymerizable polyoxyalkylene compound (A) contains a polymerizable polyoxyalkylene alkyl ether (A-1) and a polyoxyalkylene (meth) acrylate (A-2), or contains a polyoxyalkylene (meth) acrylate (A-2). (6) Furthermore, the polymerizable surface modifier described above, which contains an aliphatic alcohol. (7) A water-dispersible coating composition containing the polymerizable surface modifier described above. (8) A coated article comprising a workpiece and a cured film of the above-described coating composition formed on the surface of the workpiece. [Effects of the Invention] 【0006】 According to the present invention, a polymerizable surface modifier can be added to a water-dispersible coating composition that exhibits excellent defoaming properties (bubbling, foam suppression effect) or smoothness, and does not reduce properties such as antifogging, antistatic properties, adhesion, and hard coat properties in the cured coating film obtained by irradiation with heat or active energy rays. [Modes for carrying out the invention] 【0007】 In this specification, "(meth)acrylate" and "(meth)acrylic acid" mean "at least one selected from the group consisting of acrylates and methacrylates" and "at least one selected from the group consisting of acrylic acid and methacrylic acid," respectively. Furthermore, numerical ranges represented by "~" include the values ​​before and after that range. In this specification, "solids" means "resin concentration" in the examples. The "curing component concentration" of the water-dispersible coating composition is the concentration of compounds having (meth)acryloyl groups contained in the water-dispersible coating composition (e.g., urethane (meth)acrylate, epoxy (meth)acrylate, polyester (meth)acrylate, polyether (meth)acrylate, ethylenically unsaturated monomers, and polymerizable polyoxyalkylene compounds contained in the polymerizable surface modifier of the present invention, etc.), and does not necessarily coincide with the "resin concentration." Furthermore, in this specification, the weight-average molecular weight refers to the value measured by the method described in paragraph 30. 【0008】 [Polymerizable surface modifier] The polymerizable surface modifier in this application is used for water-dispersible coating compositions and contains a polymerizable polyoxyalkylene compound (A) represented by general formula (I) and hydrophobic silica (B). This polymerizable surface modifier is primarily used as an additive to coating compositions. It possesses excellent dispersion stability, and in particular, when used in water-dispersible coating compositions, it can be uniformly dispersed within the composition. Furthermore, it imparts excellent defoaming and / or smoothness to water-dispersible coating compositions, while maintaining and ensuring various desirable functions of the resulting coating film, such as substrate adhesion, coating hardness, anti-fogging, water and chemical resistance, and antistatic properties. Here, "for water-dispersible coating compositions" means that when 1% by mass of the polymerizable surface modifier of the present invention is contained in a water-dispersible coating composition, dispersed, and left overnight, there is no separation or sedimentation, and furthermore, when coated and cured, a coating surface without repellency or turbidity (whitening or haze) is obtained. 【0009】 (Polymerizable polyoxyalkylene compound (A)) The polymerizable polyoxyalkylene compound contained in the polymerizable surface modifier of the present invention is represented by formula (I). R 1 (-OA) n -OR 2 (I) [In the formula, R 1 This represents a group having a (meth)acryloyl group. OA represents an oxyalkylene group with 2 to 4 carbon atoms. n represents an integer between 2 and 50. If n is 2 or greater, the A's (2 or greater) may be the same or different. However, if OA is an oxyethylene group, n is between 0 and 10. R 2 This represents an alkyl group with 1 to 30 carbon atoms, an alkenyl group with 2 to 30 carbon atoms, or an acyl group with 2 to 30 carbon atoms. 【0010】 R 1The group having a (meth)acryloyl group may be a group that partially has a (meth)acryloyl group, or a group that contains it entirely, that is, the (meth)acrylate group itself. Specific examples of groups that partially have a (meth)acryloyl group include urethane (meth)acrylate groups, epoxy (meth)acrylate groups, polyester (meth)acrylate groups, and polyether (meth)acrylate groups. 【0011】 Examples of oxyalkylene groups with 2 to 4 carbon atoms in OA include oxyethylene, oxypropylene, and oxybutylene groups. Among these, oxyethylene and oxypropylene groups are preferred. If n is 2 or greater, then A's 2 or greater may be the same or different. When multiple types of oxyalkylene groups (OA) are present, their bonding configuration can be block-like, random, or a mixture thereof. Of these, the block-like configuration is preferred. Examples of multiple types of oxyalkylene groups include combinations of oxyethylene and oxypropylene groups, combinations of oxyethylene and oxybutylene groups, combinations of oxypropylene and oxybutylene groups, and combinations of oxyethylene, oxypropylene, and oxybutylene groups. Among these, the combination of oxyethylene and oxypropylene groups is preferred. In this case, the number of oxyethylene groups (-OC2H4) is preferably 0 to 10 for defoaming properties, and more preferably 0 to 5. The number of oxypropylene groups (-OC3H6) is preferably 5 or more for defoaming properties, more preferably 15 or more, and even more preferably 20 or more. In particular, a product containing 0 to 10 oxyethylene groups (-OC2H4) and 15 or more oxypropylene groups is preferred. 【0012】 R 2Examples of alkyl groups include linear alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl (lauryl), tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl (stearyl), nonadecyl, eicosyl, henicosyl, docosyl, tricosyl, tetracosyl, heptacosyl, hexaxyl, octacosyl, nonacosyl, and triaconcyl groups. Examples of branched alkyl groups include propyl, isobutyl, t-butyl, isopentyl, neopentyl, isohexyl, 2-ethylhexyl, isotridecyl, isotetradecyl, isooctadecyl, isotriaconcyl, 2-propylheptyl, 2-butyloctyl, 2-hexyldecyl, 2-octyldodecyl, 2-decyltetradecyl, 2-dodecylhexyl, 2-dodecylhexadecyl, 3,5,5-trimethylhexyl, and 3,7,11-trimethyldodecyl. Among these, alkyl groups having 1 to 20 carbon atoms are preferred, and alkyl groups having 8 to 18 carbon atoms are more preferred. R 2 Examples of alkenyl groups include linear alkenyl groups such as vinyl, allyl, propenyl, butenyl, pentenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl, icocenyl, henicocenyl, dococenyl, tricocenyl, tetracocenyl, heptacocenyl, hexaxenyl, octacocenyl, nonacocenyl, and triacontenyl, as well as branched alkenyl groups such as isobutenyl, isopentenyl, neopentenyl, isohexenyl, isotridecenyl, isooctadecenyl, and isotriacontenyl. Among these, alkenyl groups having 2 to 20 carbon atoms are preferred. R 2Examples of acyl groups include acetyl(ethanol), propanoyl, butanoyl, pentanoyl, hexanoyl, heptanol, octanoyl, nonanoyl, decanoyl, undecanoyl, dodecanoyl, tridecanoyl, tetradecanoyl, pentadecanoyl, hexadecanoyl, heptadecanoyl, octadecanoyl, nonadecanoyl, eicosanoyl, eicosanoyl, henicosanoyl, heneicosanoyl, heneicosanoyl, docosanoyl, tricasanoyl, tetracosanoyl, pentacosanoyl, hexacosanoyl, heptacosanoyl, octacosanoyl, nonacosanoyl, triacontanoyl, cyclopentanoyl, cyclohexanoyl, cycloheptanoyl Examples include saturated acyl groups such as yl, methylcyclopentanoyl, methylcyclohexanoyl, and methylcycloheptanoyl, and unsaturated acyl groups such as acryloyl, methacryloyl, crotonoyl, isocrotonoyl, butenoyl, butadienoyl, pentenoyl, hexenoyl, heptenoyl, octenoyl, nonenoyl, decenoyl, undecenoyl, dodecenoyl, tetradecenoyl, oleloyl, elaidinoyl, cyclopentenoyl, 2,4-cyclopentadienoyl, cyclohexenoyl, 2,4-cyclohexadienoyl, cycloheptenoyl, methylcyclopentenoyl, methylcyclohexenoyl, and methylcycloheptenoyl. Among these, acyl groups having 2 to 20 carbon atoms are preferred, and unsaturated acyl groups are also preferred. Among them, R 2 The preferred components are acryloyl groups, methacryloyl groups, and the like. 【0013】 Examples of polymerizable polyoxyalkylene compounds (A) include polymerizable polyoxyalkylene alkyl ethers (A-1) and polyoxyalkylene (meth)acrylates (A-2). Both polymerizable polyoxyalkylene alkyl ethers and polyoxyalkylene (meth)acrylates may be used individually or in combination of two or more types. Polymerizable polyoxyalkylene alkyl ethers (A-1) include compounds represented by formula (I-1). R 11 (-OA) n -OR2 (I-1) [During the ceremony, R 11 This represents a group that partially contains a (meth)acryloyl group. R 2 This represents an alkyl group with 1 to 30 carbon atoms, an alkenyl group with 2 to 30 carbon atoms, and an acyl group with 2 to 30 carbon atoms. OA represents an oxyalkylene group with 2 to 4 carbon atoms. n represents an integer between 2 and 50. If n is 2 or greater, the A elements 2 or greater may be the same or different. However, if OA is an oxyethylene group, n is between 0 and 10. Examples of polymerizable polyoxyalkylene alkyl ethers include, Polyoxypropylene (n=1 mole to 49 moles, e.g., 20 moles, 40 moles, etc.) butyl ether urethane (meth)acrylate, Polyoxypropylene (n=1 mole to 49 moles, e.g., 40 moles) stearyl ether urethane (meth)acrylate, Polyoxypropylene (n=1 mole to 49 moles, e.g., 40 moles) pentyl ether urethane (meth)acrylate, Polyoxyethylene polyoxypropylene (total n = 1 mole to 49 moles, e.g., 4 moles:30 moles, etc.) stearyl ether urethane (meth)acrylate, Examples include polyoxypropylene (n=1 mole to 49 moles, e.g., 40 moles) butyl ether (meth)acrylate. 【0014】 Polyoxyalkylene (meth)acrylate (A-2) is a compound represented by formula (1-2). R 12 (-OA) n -OR 2 (1-2) [During the ceremony, R 12 This represents a (meth)acryloyl group. R 2 This represents an alkyl group with 1 to 30 carbon atoms, an alkenyl group with 2 to 30 carbon atoms, and an acyl group with 2 to 30 carbon atoms. OA represents an oxyalkylene group with 2 to 4 carbon atoms. n represents an integer between 2 and 50, and if n is 2 or greater, the A values ​​2 or greater may be the same or different. 。〕 Examples of polyoxyalkylene (meth)acrylates include , Examples include polypropylene glycol (n=1 mole to 49 moles, preferably n=5 mole to 15 moles) dimethacrylate, polyethylene glycol-polypropylene glycol (total n=1 mole to 49 moles, preferably n=10 mole to 40 moles) dimethacrylate, and the like. 【0015】 In the polymerizable surface modifier of the present invention, it is preferable that the polymerizable polyoxyalkylene compound (A) contains two or more different compounds. For example, it may contain two or more polymerizable polyoxyalkylene alkyl ethers (A-1), or two or more polyoxyalkylene (meth)acrylates (A-2), or it may contain both polymerizable polyoxyalkylene alkyl ethers (A-1) and polyoxyalkylene (meth)acrylates (A-2). In particular, when both polymerizable polyoxyalkylene alkyl ethers (A-1) and polyoxyalkylene (meth)acrylates (A-2) are included, the polymerizable polyoxyalkylene alkyl ethers and polyoxyalkylene (meth)acrylates are contained in a mass ratio of, for example, 95:5 to 1:99, preferably 80:20 to 2:98, and more preferably 50:50 to 5:95. The content of the polymerizable polyoxyalkylene compound (A) in the polymerizable surface modifier is typically 80% to 99.9% by mass, preferably 90% to 99.5% by mass, and more preferably 95% to 99% by mass, relative to the solid content of the polymerizable surface modifier. 【0016】 (Hydrophobic silica (B)) Examples of hydrophobic silica (B) include silica powder or hydrophobic silica obtained by hydrophobicating hydrophilic silica with a hydrophobic agent. Hydrophobic treatment can be achieved by known methods, for example, the methods described in Japanese Patent Publication No. 42-26179 and WO2016 / 140078. Examples of hydrophobic agents include silicone oil and modified silicone oil. For silicone oil, a kinematic viscosity of 10 mm is used. 2 / s~3000mm 2 Examples include dimethylsiloxane and cyclic siloxane (octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane, etc.) at 25°C. Modified silicones include those in which some of the methyl groups of dimethylsiloxane are replaced with C2-C6 alkyl groups, C2-C4 alkoxyl groups, phenyl groups, hydrogen atoms, halogen (chlorine and bromine, etc.) atoms and / or C2-C6 aminoalkyl groups, etc. The amount of hydrophobic agent used is 5% to 70% by mass relative to the mass of silica, preferably 7% to 50% by mass, and more preferably 10% to 30% by mass. This range provides excellent defoaming properties. Alternatively, the silica may be surface-treated with dimethylsilyl groups, trimethylsilyl groups, aminoalkylsilyl groups, alkylsilyl groups, methacrylatesilyl groups, etc. Examples of hydrophobic silica available on the market include Nipsil® SS-10, SS-40, SS-50 and SS-100 (Tosoh Silica Co., Ltd.), AEROSIL® R202, R805, R812, R812S, R972, R8200, RX200, RX300 and RY200 (Nippon Aerosil Co., Ltd.), SIPERNAT® D10, D13 and D17 (Degussa Japan Co., Ltd.), TS-530, TS-610, TS-720 (Cabot Carbon Co., Ltd.), REOLOSIL® MT-10, DM-10 and DM-20S (Tokuyama Corporation), and SYLOPHOBIC® 100, 702, 505 and 603 (Fuji Silicia Chemical Co., Ltd.). Among these, SS-100 (Tosoh Silica Co., Ltd.), AEROSIL® R812, R812S, RX200, and RX300 are preferred. In other words, silica surface-modified with trimethylsilyl groups, etc., and particles with a large specific surface area are preferred. The hydrophobic silica content in the polymerizable surface modifier can range from 0.1% to 20% by mass of the total mass of the polymerizable surface modifier, with 0.5% to 10% by mass being preferred, and 1% to 5% by mass being more preferred. 【0017】 The polymerizable surface modifier in this application may further contain an aliphatic alcohol (C). The aliphatic alcohol (C) is preferably an amphiphilic (water-soluble) aliphatic alcohol having 8 to 18 carbon atoms. Specifically, this includes 1-octanol (caprylic alcohol, 8 carbon atoms), 2-ethylhexanol (8 carbon atoms), 1-nonanol (pelargon alcohol, 9 carbon atoms), isodecyl alcohol (10 carbon atoms), undecyl alcohol (11 carbon atoms), lauryl alcohol (12 carbon atoms), tridecyl alcohol (13 carbon atoms), myristyl alcohol (1-tetradecanol, 14 carbon atoms), pentadecyl alcohol (15 carbon atoms), cetanol (1-hexadecanol, 16 carbon atoms), palmitrail alcohol (cis-9-hexadecene-1-ol, 16 carbon atoms), 1-heptadecanol (17 carbon atoms), stearyl alcohol (1-octadecanol, 18 carbon atoms), isostearyl alcohol (16-methyl Examples include tilheptadecene-1-ol (18 carbon atoms), elaidyl alcohol (9E-octadecene-1-ol, 18 carbon atoms), oleyl alcohol (cis-9-octadecene-1-ol, 18 carbon atoms), linoleyl alcohol (9Z,12Z-octadecadiene-1-ol, 18 carbon atoms), eloidlinoleyl alcohol (9E,12E-octadecadiene-1-ol, 18 carbon atoms), linolenyl alcohol (9Z,12Z,15Z-octadecatriene-1-ol, 18 carbon atoms), eloidlinolenyl alcohol (9E,12E,15-E-octadecatriene-1-ol, 18 carbon atoms), ricinoleyl alcohol (12-hydroxy-9-octadecene-1-ol, 18 carbon atoms), etc. Among these, aliphatic alcohols that are liquid at room temperature are preferred, and more preferably, amphiphilic (water-soluble) aliphatic alcohols such as isodecyl alcohol, tridecyl alcohol, and stearyl alcohol. When the polymerizable surface modifier contains an aliphatic alcohol (C), its content can range from 0.1% to 80% by mass of the total mass of the polymerizable surface modifier, preferably from 1% to 60% by mass, and more preferably from 10% to 55% by mass. 【0018】 [Method for producing polymerizable surface modifiers] The polymerizable surface modifier of the present invention can be prepared by uniformly mixing a polymerizable polyoxyalkylene compound (A), hydrophobic silica (B), and optionally an aliphatic alcohol (C). These components may be mixed uniformly sequentially or all at once by known methods. Mixing is preferably carried out by dispersion treatment using an emulsifying disperser (bead mill, disper mill, homomixer, homogenizer or Gorin homogenizer, ultrasonic disperser, etc.). In this case, for example, it is preferable that the obtained polymerizable surface modifier is dispersed so that no particles larger than 100 μm are present, more preferably so that no particles larger than 70 μm are present, and even more preferably so that no particles larger than 50 μm are present. 【0019】 [Water-dispersible coating composition] The polymerizable surface modifier of the present invention can be suitably used in water-dispersible coating compositions. Specifically, by adding the above-mentioned polymerizable surface modifier to a water-dispersible coating composition, the polymerizable surface modifier can be uniformly dispersed in the water-dispersible coating composition, and its dispersibility can be stabilized. Furthermore, the polymerizable surface modifier can impart excellent defoaming properties (bubbling, foam suppression effect) and smoothness to various water-dispersible coating compositions. Moreover, when a coating film is formed using a water-dispersible coating composition and the coating film is cured with heat or active energy rays, etc., it is possible to avoid bleed-out of the polymerizable surface modifier in the coating film, and the properties such as antifogging and antistatic properties that the cured coating film of various water-dispersible coating compositions originally possesses can be maintained and ensured. The content of polymerizable surface modifier in the water-dispersible coating composition is typically 0.05% to 10% by mass, preferably 0.1% to 5% by mass, and more preferably 0.5% to 3% by mass, relative to the total mass of the water-dispersible coating composition. 【0020】 The water-dispersible coating composition may be any composition used in the field, as long as it contains a water-soluble polymer compound as a base material. Examples include water dispersions of urethane acrylate, epoxy acrylate, poly(meth)acrylate, polyurethane, polyacrylamide, polyethylene oxide, polyvinylpyrrolidone, polyvinyl alcohol, polyvinylamide, polyamine, epoxy resin, cellulose resin, phenolic resin, etc. 【0021】 The water-dispersible coating composition of the present invention may contain an antistatic agent in addition to the polymerizable surface modifier described above. This synergistically enhances the antistatic effect of the cured polymer when the water-dispersible coating composition is crosslinked and polymerized, significantly improving the antistatic effect. Furthermore, by setting the content of the antistatic agent to, for example, the following range, a sufficient antistatic effect can be obtained without the antistatic agent being lost from the cured polymer during crosslinking and polymerization. Examples of antistatic agents include at least one electronically conductive antistatic agent selected from π-conjugated conductive polymers such as polythiophenes, polyanilines, polythiophene vinylenes, polypyrroles, and polyfurans; a cationic antistatic agent of quaternary ammonium salts; at least one anionic antistatic agent selected from aliphatic sulfonates, higher alcohol sulfate esters, higher alcohol alkylene oxide adduct sulfate esters, higher alcohol phosphate esters, and higher alcohol alkylene oxide adduct phosphate esters; and at least one nonionic antistatic agent selected from higher alcohol alkylene oxide adducts and polyalkylene glycol fatty acid esters. Among these, crosslinked electronically conductive antistatic agents mainly composed of PEDOT / PSS are preferred. The amount of the antistatic agent is 0 to 10% by mass relative to the solid content of the water-dispersible coating composition, preferably 0.01% to 5% by mass, more preferably 0.05% to 5% by mass, and particularly preferably 0.1% to 5% by mass. 【0022】 Furthermore, the water-dispersible coating composition of the present invention may contain ethylenically unsaturated monomers, photopolymerization initiators, photopolymerization initiator aids, thermal polymerization catalysts, fillers, dyes and pigments, plasticizers, drying agents, dispersants, wetting agents, emulsifiers, gelling agents, stabilizers, thixotropy-imparting agents, antioxidants, flame retardants, antistatic agents, insecticides, fungicides, mite repellents, fillers, reinforcing agents, matting agents, crosslinking agents, and the like. Any of these commonly used in the art may be used. 【0023】 (Ethylene-unsaturated monomer) Examples of ethylenically unsaturated monomers to be added to water-dispersible coating compositions include (meth)acrylic acid compounds and vinyl group-containing compounds. Examples of (meth)acrylic acid compounds include acrylamides, alkyl (meth)acrylates, aminoalkyl (meth)acrylates, quaternary salts of aminoalkyl (meth)acrylates, alkoxy polyalkylene glycol (meth)acrylates, hydroxyalkyl (meth)acrylates, acid anhydride adducts of hydroxyalkyl (meth)acrylates, polyalkylene glycol di(meth)acrylates, alkyldiol di(meth)acrylates, polyol poly(meth)acrylates, alkylene oxide-added polyol poly(meth)acrylates, etc. Examples of vinyl group-containing compounds include vinyl acetate, N-vinylacetamide, vinylpyrrolidone, vinyl alkyl ethers, vinyl sulfonic acid, and salts of vinyl sulfonic acid. These may be used individually or in combination of two or more. 【0024】 Examples of acrylamides include (meth)acryloylmorpholine and dimethylaminoalkyl(meth)acrylamide. Examples of aminoalkyl(meth)acrylates include diethylaminoethyl(meth)acrylate. Examples of quaternary salts of aminoalkyl(meth)acrylates include alkyloylaminopropyldimethyl-2-hydroxyethylammonium salt. Examples of alkyl(meth)acrylates include methyl(meth)acrylate, ethyl(meth)acrylate, and propyl(meth)acrylate. Examples of alkoxypolyalkylene glycol(meth)acrylates include methoxypolyethylene glycol(meth)acrylate and methoxypolypropylene glycol(meth)acrylate. Examples of hydroxyalkyl(meth)acrylates include hydroxyethyl(meth)acrylate and hydroxypropyl(meth)acrylate. Examples of acid anhydride adducts of hydroxyalkyl (meth)acrylate include hydroxyethyl (meth)acrylate phthalic anhydride adduct, hydroxyethyl (meth)acrylate succinic anhydride adduct, hydroxyethyl (meth)acrylate tetrahydrophthalic anhydride adduct, hydroxyethyl (meth)acrylate hexahydrophthalic anhydride adduct, hydroxypropyl (meth)acrylate phthalic anhydride adduct, hydroxypropyl (meth)acrylate succinic anhydride adduct, hydroxypropyl (meth)acrylate tetrahydrophthalic anhydride adduct, and hydroxypropyl (meth)acrylate hexahydrophthalic anhydride adduct. Examples of polyalkylene glycol di(meth)acrylates include polyethylene glycol di(meth)acrylate and polypropylene glycol di(meth)acrylate. Examples of alkyldiol di(meth)acrylates include butanediol di(meth)acrylate and hexanediol di(meth)acrylate.Examples of polyol poly(meth)acrylates include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, and dipentaerythritol hexa(meth)acrylate. Examples of alkylene oxide-added polyol poly(meth)acrylates include alkylene oxide-added trimethylolpropane tri(meth)acrylate, alkylene oxide-added pentaerythritol tri(meth)acrylate, alkylene oxide-added pentaerythritol tetra(meth)acrylate, and alkylene oxide-added pentaerythritol hexa(meth)acrylate. Examples of vinyl alkyl ethers include methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, amyl vinyl ether, and 2-ethylhexyl vinyl ether. In particular, the (meth)acrylic acid compound or vinyl group-containing compound is more preferably (meth)acryloylmorpholine, vinylpyrrolidone, dimethylaminoalkyl (meth)acrylate, quaternary salt of dimethylaminoalkyl (meth)acrylate, dimethylaminoalkyl (meth)acrylamide, N-vinylacetamide, vinyl sulfonic acid, and vinyl sulfonate, as these compounds are water-soluble and provide adhesion to plastic substrates. The ethylenically unsaturated monomer can be present in an amount of 0 to 100% by mass relative to the curing component in the water-dispersible coating composition, with 0.02% to 80% by mass being preferred. 【0025】 (Photopolymerization initiator) The photopolymerization initiator is not particularly limited as long as it generates radicals upon the action of light, for example, 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-(4-isopropylenephenyl)-2-hydroxy-2-methylpropan-1-one, 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-(2-hydroxyethoxy)-phenyl(2-hydroxy-2-propyl)ketone, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyldimethyl Examples include ketal, benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3'-dimethyl-4-methoxybenzophenone, thioxanthone, 2-chlorthioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, camphorquinone, dibenzosverone, 2-ethylanthraquinone, 4',4"-diethylisophthalophenone, 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone, α-acyloxime ester, acylphosphine oxide, methylphenylglyoxylate, benzyl, 9,10-phenanthylenequinone, and 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)ketone. In particular, to better exhibit the function of the water-dispersible coating composition, it is preferable to use a water-soluble or water-dispersible photopolymerization initiator. Examples of such photopolymerization initiators include 2-(3-dimethylamino-2-hydroxypropoxy)-3,4-dimethyl-9H-thioxanthone-9-one metochloride (Octel Chemicals, "Quantacure QTX"), 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one (Ciba Specialty Chemicals, "Irgacure 2959"), and among these, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one (Ciba Specialty Chemicals, "Irgacure 2959" and IGMresins BV, "Omnirad 2959") are more preferred. The amount of the photopolymerization initiator relative to the curing component of the water-dispersible coating composition is typically 0.002% to 10% by mass, preferably 0.01% to 10% by mass, more preferably 0.05% to 8% by mass, and particularly preferably 0.6% to 5% by mass. 【0026】 (Photopolymerization initiator) A photopolymerization initiator may be used in combination with a photopolymerization initiator. Examples of photopolymerization initiators include triethanolamine, triisopropanolamine, 4,4'-dimethylaminobenzophenone (Michler ketone), 4,4'-diethylaminobenzophenone, 2-dimethylaminoethylbenzoic acid, 4-dimethylaminobenzoate ethyl, 4-dimethylaminobenzoate (n-butoxy)ethyl, 4-dimethylaminobenzoate isoamyl, 4-dimethylaminobenzoate 2-ethylhexyl, 2,4-diethylthioxanthone, and 2,4-diisopropylthioxanthone. 【0027】 (Thermal polymerization catalyst) Examples of thermal polymerization catalysts include radical polymerization initiators that cause addition polymerization of vinyl monomers by radical decomposition using heat or reducing substances. For example, water-soluble persulfates, peroxides, and azobis compounds are preferred. Specifically, examples include potassium persulfate, sodium persulfate, ammonium persulfate, hydrogen peroxide, t-butyl hydroperoxide, t-butyl peroxybenzoate, 2,2-azobisisobutyronitrile, 2,2-azobis(2-diaminopropane)hydrochloride, and 2,2-azobis(2,4-dimethylvaleronitrile). Among these, potassium persulfate, sodium persulfate, and ammonium persulfate are preferred. The amount of thermal polymerization catalyst relative to the curing component of the water-dispersible coating composition is 0.001% to 10% by mass, preferably 0.01% to 10% by mass, more preferably 0.05% to 8% by mass, and even more preferably 0.6% to 5% by mass. When accelerating the polymerization rate and polymerization at low temperatures such as 70°C or below are desired, it is advantageous to use reducing agents such as sodium bisulfite, ferrous chloride, ascorbate, and rongalit in combination with radical polymerization initiators. 【0028】 The water-dispersible coating composition of the present invention may contain an organic solvent. Examples of organic solvents include propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, and cellosolves. If the water-dispersible coating composition of the present invention contains an organic solvent, the content thereof can be 0.0001% to 5% by mass, preferably 0.001% to 2% by mass, and more preferably 0.001% to 1% by mass, relative to the total mass of the water-dispersible coating composition. 【0029】 The water-dispersible coating composition of the present invention can be applied to substrates such as plastics (e.g., polyolefin resins such as polyethylene, polypropylene, and polycyclopentadiene, polycarbonate, polyester, ABS resin, acrylic resin, etc.), glass, paper, wood, cement, etc., and then crosslinked / polymerized by irradiation with light rays such as far ultraviolet, ultraviolet, near ultraviolet, and infrared rays, or active energy rays such as X-rays and gamma rays. When a water-dispersible coating composition is applied to the surface of an object to be coated to form a cured film, its thickness is typically 1 μm to 50 μm, preferably 2 μm to 10 μm. Methods for applying a water-dispersible coating composition to any surface of a substrate include, for example, methods using coaters such as gravure coaters, roll coaters, curtain flow coaters, spin coaters, bar coaters, reverse coaters, kiss coaters, fountain coaters, rod coaters, air doctor coaters, knife coaters, blade coaters, cast coaters, and screen coaters; methods using sprayers such as air sprayers, airless sprayers, and rotor dampening devices; and immersion methods such as dipping. After applying a water-dispersible coating composition to a substrate, the coating film is cured by irradiation with active energy rays, heat treatment, or a combination of both. Examples of active energy rays include far-ultraviolet, ultraviolet, near-ultraviolet, and infrared rays, as well as X-rays and gamma rays. The irradiation dose of active energy rays is, for example, 100 mJ / cm². 2 ~2000 mJ / cm 2 The range is 500 mJ / cm². 2 ~1000 mJ / cm 2 The range is preferred. Heat treatment may include hot air drying and heat treatment at a temperature range of 60°C to 200°C, specifically at a temperature range of 80°C to 200°C for 1 to 30 minutes, with 5 to 15 minutes at 100°C, 3 to 10 minutes at 120°C, and 1 to 5 minutes at 130°C or 150°C being more preferred. When heat-curing a water-dispersible coating composition, it is preferable to perform hot air drying and heat treatment for 1 to 30 minutes in a temperature range of 80°C to 200°C or lower, and more preferably 15 minutes at 100°C, 5 minutes at 120°C, and 1 to 5 minutes at 150°C. By drying at a relatively high temperature and for a short time, the leveling properties of the coating surface are improved, and the resistance to steel wool can also be enhanced. The water-dispersible coating composition of the present invention contains the polymerizable surface modifier of the present invention, and the polymerizable surface modifier is uniformly and stably dispersed in the water-dispersible coating composition, and while it has good defoaming properties (bubbling and anti-foaming effect) and smoothness, it can maintain and ensure the excellent properties that the cured coating film of the water-dispersible coating composition originally possesses, such as substrate adhesion, coating hardness, anti-fogging properties, water resistance and chemical resistance, and water-resistant antistatic properties. [Examples] 【0030】 The embodiments of the present invention will be described in detail below. Note that the weight-average molecular weight refers to the weight-average molecular weight converted to the standard polystyrene molecular weight, and can be measured by using a high-performance liquid chromatography system (Showa Denko Corporation, "Shodex GPC system 11") with three Shodex GPC KF-806L columns in series (exclusion limit molecular weight: 2 × 10⁷, separation range: 100 to 2 × 10⁷, theoretical plates: 10,000 plates / column, packing material: styrene-divinylbenzene copolymer, packing particle size: 10 μm). The polymerizable polyoxyalkylene compound (A) of the present invention was specifically produced as follows. Synthesis Example 1: Preparation of Polyoxypropylene Butyl Ether Urethane Acrylate (DUA-1) In a four-necked flask equipped with a thermometer, stirrer, and water-cooled condenser, 2397.86 g (1.0 mol) of polyoxypropylene (40 mol) butyl ether (PPG-40 butyl) (weight-average molecular weight 2397.86, hydroxyl value 23.4 mg KOH / g), 141.12 g (1.0 mol) of 2-acryloyloxyethyl isocyanate (manufactured by Resonaq Corporation, Karenz AOI, weight-average molecular weight 141.12), 1.0 g of 2,6-di-tert-butyl cresol, and 0.25 g of dibutyltin dilaurate were charged, and the mixture was reacted at 55°C for approximately 1 hour. Since the reaction generates a large amount of heat once it begins, it was cooled as needed. Once the heat generation had almost subsided, the mixture was heated to 70°C and reacted for 3 hours. The infrared absorption spectrum of the oligomer was measured, and the absorption spectrum of the isocyanate group (2280 cm²) was measured. -1 The reaction was terminated when the substance disappeared, and polyoxypropylene (40 mol) butyl ether urethane acrylate (DUA-1) was obtained (resin concentration 100%). 【0031】 Synthesis Example 2: Preparation of Polyoxypropylene Butyl Ether Urethane Methacrylate (DUMA-1) In Synthesis Example 1, instead of 141.12 g (1.0 mol) of 2-acryloyloxyethyl isocyanate (manufactured by Resonaq Corporation, Karenz AOI, weight-average molecular weight 141.12), 155.15 g (1.0 mol) of 2-methacryloyloxyethyl isocyanate (manufactured by Resonaq Corporation, Karenz MOI, weight-average molecular weight 155.15) was charged, and the reaction was carried out in the same manner as in Synthesis Example 1 to obtain polyoxypropylene (40 mol) butyl ether urethane methacrylate (DUMA-1) (resin concentration 100%). 【0032】 Synthesis Example 3: Preparation of Polyoxypropylene Butyl Ether Urethane Acrylate (DUA-2) In Synthesis Example 1, instead of using 2397.86 g (1.0 mol) of polyoxypropylene (40 mol) butyl ether (PPG-40 butyl) (weight-average molecular weight 2397.86, hydroxyl value 23.4 mg KOH / g), 1201.5 g (1.0 mol) of polyoxypropylene (20 mol) butyl ether (PPG-20 butyl) (weight-average molecular weight 1201.5, hydroxyl value 46.7 mg KOH / g) was used. After charging 0.5 g of 2,6-di-tert-butyl cresol and 0.13 g of dibutyltin dilaurate, the reaction was carried out in the same manner as in Synthesis Example 1 to obtain polyoxypropylene (20 mol) butyl ether urethane acrylate (DUA-2) (resin concentration 100%). 【0033】 Synthesis Example 4: Preparation of Polyoxyethylene Polyoxypropylene Stearyl Ether Urethane Acrylate (DUA-3) In Synthesis Example 1, 2397.86 g (1.0 mol) of polyoxypropylene (40 mol) butyl ether (PPG-40 butyl) (weight-average molecular weight 2397.86, hydroxyl value 23.4 mg KOH / g) was replaced with 1541.5 g (1.0 mol) of polyoxyethylene (4 mol) polyoxypropylene (30 mol) stearyl ether (PPG-30 steareth-4) (weight-average molecular weight 1541.5, hydroxyl value 36.4 mg KOH / g). This was reacted in the same manner as in Synthesis Example 1 to obtain polyoxyethylene (4 mol) polyoxypropylene (30 mol) stearyl ether urethane acrylate (DUA-3) (resin concentration 100%). 【0034】 Synthesis Example 5: Preparation of Polyoxypropylene Butyl Ether Acrylate (DA-1) In a four-necked flask equipped with a thermometer, stirrer, and water-cooled condenser, 2397.86 g (1.0 mol) of polyoxypropylene (40 mol) butyl ether (PPG-40 butyl) (weight-average molecular weight 2397.86, hydroxyl value 23.4 mg KOH / g), 138.6 g (1.1 mol) of acrylic anhydride, and 17.4 g of methanesulfonic acid were charged, and the mixture was reacted at 60°C for 8 hours. The resulting reaction solution was cooled to room temperature, 5225.1 g of toluene was charged, and the mixture was washed twice with 600 g of 5% sodium hydroxide aqueous solution, followed by three washes with 700 g of deionized water. Toluene was removed by distillation under reduced pressure at 60°C and 20 torr to obtain polyoxypropylene (40 mol) butyl ether acrylate (DA-1) (resin concentration 100%). 【0035】 Comparative Synthesis Example 6: Preparation of Polyoxyethylene Polyoxypropylene Stearyl Ether Urethane Acrylate (DUA-4) In Synthesis Example 1, 2397.86 g (1.0 mol) of polyoxypropylene (40 mol) butyl ether (PPG-40 butyl) (weight-average molecular weight 2397.86, hydroxyl value 23.4 mg KOH / g) was replaced with 3087.13 g (1.0 mol) of polyoxyethylene (34 mol) polyoxypropylene (23 mol) stearyl ether (PPG-23 steareth-34) (weight-average molecular weight 3087.13, hydroxyl value 18.2 mg KOH / g). This mixture was heated to 40°C and charged, and reacted in the same manner as in Synthesis Example 1 to obtain polyoxyethylene (34 mol) polyoxypropylene (23 mol) stearyl ether urethane acrylate (DUA-4) (resin concentration 100%). 【0036】 Comparative Synthesis Example 7: Preparation of Polyoxyethylene Isostearyl Ether Urethane Acrylate (DUA-5) In Synthesis Example 1, 2397.86 g (1.0 mol) of polyoxypropylene (40 mol) butyl ether (PPG-40 butyl) (weight-average molecular weight 2397.86, hydroxyl value 23.4 mg KOH / g) was replaced with 975.35 g (1.0 mol) of polyoxyethylene (16 mol) isostearyl ether (isosteareth-16) (weight-average molecular weight 975.35, hydroxyl value 57.5 mg KOH / g). This mixture was heated to 40°C and charged, then reacted in the same manner as in Synthesis Example 1 to obtain polyoxyethylene (16 mol) isostearyl ether urethane acrylate (DUA-5) (resin concentration 100%). 【0037】 Example 1: Production of polymerizable surface modifier (RS-1) As the polymerizable polyoxyalkylene compound (A), 10% by mass of polyoxypropylene butyl ether urethane acrylate (DUA-1) and 87% by mass of polypropylene glycol dimethacrylate (manufactured by NOF Corporation, PDP-400N) were used. Furthermore, 3% by mass of hydrophobic silica (B), AEROSIL® R812S (Nippon Aerosil Co., Ltd.), was added and stirred at 25°C for 30 minutes. Then, using a homomixer (manufactured by PRIMIX), the mixture was stirred at 8000 rpm for 3 hours while cooling to 25°C to obtain a homogeneous dispersion. A dispersion test (JIS K5600-2-5:1999 (corresponding to ISO 1524:1983)) confirmed that there were no particles larger than 50 microns, and polymerizable surface modifier (RS-1) was obtained. 【0038】 Example 2: Production of polymerizable surface modifier (RS-2) As polymerizable polyoxyalkylene compound (A), 10% by mass of polyoxypropylene butyl ether urethane acrylate (DUA-1) and 40% by mass of polypropylene glycol dimethacrylate (manufactured by NOF Corporation, PDP-400N) were used. Furthermore, 3% by mass of hydrophobic silica (B) AEROSIL® R812S (Nippon Aerosil Co., Ltd.) and 47% by mass of isodecyl alcohol (C) were added to obtain a homogeneous dispersion in the same manner as in Example 1. 【0039】 Surface modifiers (RS-1 to RS-13 and S14 to S15) were prepared in the same manner as in Examples 1 and 2 by blending the components shown in Tables 1 to 4 below. [Table 1] [Table 2] [Table 3] [Table 4] The abbreviations for each component in Tables 1-4 are as follows: PDP-400N (manufactured by NOF Corporation, polypropylene glycol (PPG, 7 mol) dimethacrylate) 40PDC-1700B (manufactured by NOF Corporation, polyethylene glycol (PEG, 7.5 mol) - polypropylene glycol (PPG, 17 mol) dimethacrylate) 9EG-A (manufactured by Kyoeisha Chemical, Light Acrylate 9EG-A, polyethylene glycol (9 mol) diacrylate) PPG-40 Butyl:Polyoxypropylene (40 mol) Butyl Ether (Weight-average molecular weight 2397.86, hydroxyl value 23.4 mgKOH / g) Cosmo SC22 (mineral oil, manufactured by Cosmo Oil Co., Ltd., kinematic viscosity (40℃) 22mm) 2 / s) B-1: AEROSIL L812S (Aerosil Japan Co., Ltd.) B-2: NipsilSS-100 (Tosoh Silica Co., Ltd.) C-1: Isodecyl alcohol C-2: Tridecyl alcohol 【0040】 Test Example 1: Dispersion Stability of Surface Modifiers The obtained surface modifiers RS-1 to 13 and S14 to 15 were left to stand at room temperature, and their dispersion stability was observed visually. The results are shown in Table 5. ○: No separation or sedimentation even after 2 days (homogeneous solution) ×: Leaving it overnight can cause separation and sedimentation. [Table 5] 【0041】 Test Example 2: Characterization of a water-dispersible coating composition To the total mass of the water-dispersible UV hard coat agent "UAW-HC10" (manufactured by Kyoeisha Chemical, 33% solids [33% curing component], containing a photopolymerization initiator), 1% by mass of the surface modifier obtained in the examples and comparative examples that were evaluated as having good dispersion stability (〇) in Test Example 1 was added and dissolved, and the following tests were performed. (defoaming) 1. 30g of the sample was placed in a 100ml poly cup and dispersed in a φ30mm disperser at 1000rpm for 3 minutes. 2. The foam was removed using a centrifugal degasser for 2 minutes. 3. 15g of the degassed sample was placed in a Maruemu screw tube No. 7 white (Sansho Co., Ltd., capacity: 50ml, body diameter 35mm, total length 78mm), and shaken for 10 minutes in a paint shaker (FAST&FLUID MANEGEMENT, shaker SK550 1.1) to induce foaming again. The defoaming properties (height of foaming) after 10 minutes were compared with those of a sample without surface modifiers. (Leveling properties) A PET substrate (hereinafter referred to as easy-adhesion polyester film, manufactured by Toyobo, CosmoShine® A-4160, thickness 125 μm) was coated using a bar coater #14 to achieve a dry film thickness of 3 μm. After coating with each emulsion, drying and heat treatment were performed at 80°C for 3 minutes, and irradiation was performed using an electrodeless lamp H bulb at a line speed of 5.4 m / min and an irradiation dose of 600 mJ / cm². 2 , Peak illuminance: 1,500mW / cm 2 Ultraviolet irradiation was performed. The leveling properties were visually assessed based on the appearance of the resulting cured coating. ○: Good smoothness ×: Removal or shrinkage may occur. (Adhesion to substrate) Various plastic substrates (PET, ABS, PC, PMMA) were coated using a bar coater #14 to achieve a dry film thickness of 3 μm. After coating each emulsion, drying and heat treatment were performed at 80°C for 3 minutes, and irradiation was performed using an electrodeless lamp H bulb at a line speed of 5.4 m / min and an irradiation dose of 600 mJ / cm². 2 , Peak illuminance: 1,500mW / cm 2 UV irradiation was performed. After being left overnight in a constant temperature and humidity chamber at 23°C and 32%RH, the adhesion to various substrates was evaluated. In accordance with JIS K5400, 100 grids of 2 mm squares were made on the cured coating film, and an adhesion test was performed using cellophane tape. The peeling state of the grid was observed, and the number of remaining squares was measured. (Coating film hardness) The pencil hardness of the polyester film with a cured coating was measured in accordance with JIS K5400. These results are shown in Table 6. [Table 6] 【0042】 Test Example 3 To the total mass of the water-dispersible anti-fogging coating agent "UAW-AF132MS" (manufactured by Kyoeisha Chemical, 23% solids [6% curing component], containing a photopolymerization initiator), 1% by mass of the surface modifier obtained in the examples and comparative examples that were evaluated as having good dispersion stability (〇) in Test Example 1 was added, and the mixture was dispersed and dissolved as described in (Defoaming) 1. A PC substrate (transparent polycarbonate sheet, manufactured by Takiron CI Co., Ltd., PC-1600, dimensions: 2.0 x 75 x 150 mm) was coated using a bar coater #14 to achieve a dry film thickness of 3 μm to 5 μm. After coating with each emulsion, drying and heat treatment were performed at 100°C for 5 minutes, and irradiation was performed using an electrodeless lamp H bulb at a line speed of 5.4 m / min and an irradiation dose of 600 mJ / cm². 2 , Peak illuminance: 1,500mW / cm 2 Ultraviolet irradiation was performed. The following tests were conducted on PC panels with an anti-fogging coating as part of the anti-fogging performance test. The results are shown in Table 7. (Anti-fogging properties from exhalation) Exhaled breath was blown onto the surface of the coating at room temperature, and the presence or absence of fogging was visually evaluated. Mark with a circle (○) if no cloudiness is observed. Items showing cloudiness were marked with an "X". (Steam anti-fog) A container was filled with 60°C hot water to a height of 1 cm above the water surface. The container was then covered with a film with the anti-fog coating facing downwards, and the presence or absence of fogging of the coating was visually evaluated after 2 minutes. Mark with a circle (○) if no cloudiness is observed. △ indicates that the fog is visible for approximately 10 seconds, and then disappears. Items showing cloudiness were marked with an "X". (Water traces remain) After steam anti-fogging treatment, the test specimens were propped up at a 90° angle and left to dry overnight indoors. The appearance of the test specimens was then visually evaluated. A circle (○) indicates that no traces of water droplets have been observed. Marked with a triangle (△) if the sagging marks are only visible as an outline. We marked samples with a white, overall bleed-out appearance as "X". [Table 7] 【0043】 Test Example 4 To the total mass of the water-dispersible untreated PET primer coating agent "UAW-PET200" (manufactured by Kyoeisha Chemical, solids content 20% [curing component 10%]), 0.5% by mass of ammonium persulfate (APS) as a thermal polymerization catalyst and 1% by mass of the surface modifier obtained in the examples and comparative examples that were evaluated as having good dispersion stability (〇) in Test Example 1 were added, and the mixture was dispersed and dissolved as described in (Defoaming) 1. An untreated PET substrate (Toray Industries, Ltd., Lumirror® T60-A4, 125 μm thick) was coated using a bar coater #14 to achieve a dry film thickness of 3 μm. After coating with each emulsion, drying and heat curing were performed at 150°C for 5 minutes. The following additional tests were conducted on the polyester film with the cured coating. The results are shown in Table 8. (Water-resistant, chemical-resistant) After wiping the hardened coating surface of the test piece obtained above 10 times with a cloth (Crecia Technowipe C100-S (manufactured by Nippon Paper Crecia Co., Ltd.)) impregnated with water, ethanol, and MEK (methyl ethyl ketone), respectively, the piece was dried for 1 hour at 25°C and then visually evaluated. ○: No scratches on the sample surface, and no change in transparency. ×: Scratches and whitening are visible on the sample surface. [Table 8] 【0044】 Test Example 5 To the total mass of the water-dispersible UV-curable antistatic coating agent "UAW-AS640" (manufactured by Kyoeisha Chemical, solids content 26% [curing component 24%], containing a photopolymerization initiator), 1% by mass of the surface modifier obtained in the examples and comparative examples that were evaluated as having good dispersion stability (〇) in Test Example 1 was added, and the mixture was dispersed and dissolved as described in (Defoaming) 1. A PET substrate (hereinafter referred to as easy-adhesion polyester film, manufactured by Toyobo, CosmoShine® A-4160, thickness 125 μm) was coated using a bar coater #14 to achieve a dry film thickness of 5 μm. After coating with each emulsion, drying and heat treatment were performed at 130°C for 2 minutes, and irradiation was performed using an electrodeless lamp H bulb at a line speed of 5.4 m / min and an irradiation dose of 600 mJ / cm². 2 , Peak illuminance: 1,500mW / cm 2 Ultraviolet irradiation was performed. The following tests were conducted using the obtained polyester film with an antistatic coating. The results are shown in Table 9. (Initial antistatic properties) High-Lester UX applied voltage: 250V The surface resistivity (Ω / sq.) was measured under a measurement environment of 20℃ and 45%RH. Surface resistivity: 1×10 5 Ω / sq. ~ 1 × 10 11 A value of Ω / sq. was considered to indicate antistatic properties (○). Surface resistivity: 1×10 12 A value of Ω / sq. or higher was considered to have no antistatic properties (marked with ×). (Water-resistant and anti-static) A polyester film with an antistatic coating was immersed in running water for 10 minutes, then the water droplets were wiped off with a cloth, and the film was left to stand for 1 hour under the measurement conditions of 20°C and 45% RH. Subsequently, the surface resistivity (Ω / sq.) was measured under a measurement environment of 20°C and 45% RH with a Hi-Lester UX applied voltage of 250V. It has initial antistatic properties, Select items where no increase in surface resistivity is observed after the water resistance test. The increase in surface resistivity after the water resistance test is 1 × 10⁻⁶. 1 △ indicates a certain degree. Items with a surface resistivity increase of 1 × 10 < after the water resistance test are marked with an asterisk (×). If the coating peeled or ran from the substrate after the water resistance test, or turned white, it was designated as XX. [Table 9] 【0045】 Test Example 6 To the total mass of an aqueous dispersion of water-soluble epoxy (meth)acrylate EW (weight-average molecular weight: 6000, solids content 30% [curing component 30%]), 1.2% by mass of a photopolymerization initiator (Omnirad 2959, manufactured by IGMResins BV) and 1% by mass of a surface modifier obtained from examples and comparative examples that were evaluated as having good dispersion stability (〇) in Test Example 1 were added, and the mixture was dispersed and dissolved as described in (Defoaming) 1. A PET substrate (hereinafter referred to as easy-adhesion polyester film, manufactured by Toyobo, CosmoShine® A-4160, thickness 125 μm) was coated using a bar coater #14 to achieve a dry film thickness of 5 μm. After coating each emulsion, drying and heat treatment were performed at 80°C for 5 minutes, and irradiation was performed using an electrodeless lamp H bulb at a line speed of 5.4 m / min and an irradiation dose of 600 mJ / cm². 2 , Peak illuminance: 1,500mW / cm 2 Ultraviolet irradiation was performed. The same test was performed using the resulting cured polyester film. The results are shown in Table 10. [Table 10] The polymerizable surface modifier of the present invention has been confirmed to have excellent dispersion stability. Furthermore, it has been confirmed that the water-dispersible coating composition containing the polymerizable surface modifier of the present invention exhibits good defoaming properties (bubbling and anti-foaming effect) and smoothness, while also maintaining and ensuring the excellent properties of the cured coating film of the water-dispersible coating composition that it originally possessed, such as substrate adhesion, coating film hardness, anti-fogging properties, water and chemical resistance, and water-resistant antistatic properties. [Industrial applicability] 【0046】 The polymerizable surface modifier of the present invention and various water-dispersible coating compositions containing it are extremely useful as various film-forming materials such as paints, adhesives, glues, adhesive smears, release agents, inks, protective coatings, anchor coatings, magnetic powder coating binders, sandblasting coatings, and printing plates. Furthermore, the coated articles of the present invention have excellent scratch resistance, antistatic properties, anti-fogging properties, and water and chemical resistance, and can be used on a variety of substrates.

Claims

[Claim 1] A polymerizable surface modifier for water-dispersible coating compositions containing a polymerizable polyoxyalkylene compound (A) represented by general formula (I) and hydrophobic silica (B). R 1 (-OA) n -OR 2 (I) [During the ceremony, R 1 This represents a group having a (meth)acryloyl group. R 2 This represents an alkyl group having 1 to 30 carbon atoms or an acyl group having 2 to 30 carbon atoms. OA represents an oxyalkylene group with 2 to 4 carbon atoms. n represents an integer between 2 and 50. If n is 2 or greater, the A elements (2 or greater) may be the same or different. However, OA is not limited to oxyethylene groups. [Claim 2] The polymerizable surface modifier according to claim 1, wherein the polymerizable polyoxyalkylene compound (A) comprises one or more selected from the group consisting of polymerizable polyoxyalkylene alkyl ethers (A-1) and polyoxyalkylene (meth)acrylates (A-2). [Claim 3] The polymerizable surface modifier according to claim 2, wherein the polymerizable polyoxyalkylene alkyl ether (A-1) is a compound represented by formula (I-1), and the polyoxyalkylene (meth)acrylate (A-2) is a compound represented by formula (I-2). R 11 (-OA) n -OR 2' (I-1) R 12 (-OA) n -OR 2 (I-2) [During the ceremony, R 11 This represents a group that partially contains a (meth)acryloyl group. R 12 This represents a (meth)acryloyl group. R2' represents an alkyl group having 1 to 30 carbon atoms. R 2 This represents an alkyl group having 1 to 30 carbon atoms or an acyl group having 2 to 30 carbon atoms. OA represents an oxyalkylene group with 2 to 4 carbon atoms. n represents an integer between 2 and 50. If n is 2 or greater, the A elements (2 or greater) may be the same or different. However, OA is not limited to oxyethylene groups. [Claim 4] The polymerizable surface modifier according to claim 1, comprising two or more different compounds as the polymerizable polyoxyalkylene compound (A). [Claim 5] The polymerizable surface modifier according to claim 3, wherein the polymerizable polyoxyalkylene compound (A) comprises a polymerizable polyoxyalkylene alkyl ether (A-1) and a polyoxyalkylene (meth)acrylate (A-2), or comprises a polyoxyalkylene (meth)acrylate (A-2). [Claim 6] Furthermore, the polymerizable surface modifier according to claim 1, further comprising an aliphatic alcohol. [Claim 7] A water-dispersible coating composition comprising a polymerizable surface modifier according to any one of claims 1 to 6. [Claim 8] The object to be coated and A coated article comprising a cured film of the coating composition according to claim 7 formed on the surface of the object to be coated.

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