Coating agent, cured product, and laminate

Abstract

To provide a coating agent, a cured product, and a laminate.SOLUTION: A coating agent contains a poly(meth)acrylate and a multibranched filler, the proportion of the multibranched filler with respect to 100 mass% of nonvolatile matter being from 15 mass% to 90 mass%.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present disclosure relates to coatings, cured products, and laminates. [Background technology]

[0002] Active energy ray-curable compositions are used in various fields such as coating agents (for example, Patent Document 1). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Special Publication No. 62-021815 Summary of the Invention [Problem to be solved by the invention]

[0004] The problem to be solved by the present invention is to provide a coating agent that can produce a cured product with good initial water repellency. [Means for solving the problem]

[0005] The present disclosure provides the following: (Item 1) A coating agent, The coating agent includes a poly(meth)acrylate and a hyperbranched filler, The coating agent has a content of the multi-branched filler of 15% by mass to 90% by mass relative to 100% by mass of nonvolatile matter. (Item 2) The coating agent according to the preceding item, wherein the poly(meth)acrylate contains silicone units and / or perfluoroalkyl units. (Item 3) A cured product of the coating agent according to any one of the above items. (Item 4) A laminate comprising the cured product described in the above item.

[0006] In the present disclosure, one or more of the above-described features may be provided in further combinations in addition to the combinations explicitly stated. [Effects of the Invention]

[0007] The cured product of the present invention exhibits good initial water repellency. DETAILED DESCRIPTION OF THE INVENTION

[0008] Throughout this disclosure, the range of the values ​​of the physical properties, contents, etc. may be set as appropriate (for example, by selecting from the values ​​described in each item below). Specifically, when the value α includes A3, A2, A1 (where A3>A2>A1), the range of the value α may include A3 or less, A2 or less, less than A3, less than A2, A1 or more, A2 or more, greater than A1, greater than A2, A1 to A2 (A1 or more and less than A2), A1 to A3, A2 to A3, A1 or more and less than A3, A1 or more and less than A2, A2 or more and less than A3, greater than A1 and less than A3, greater than A1 and less than A2, greater than A2 and less than A3, greater than A1 ... and the like.

[0009] As long as the problem to be solved by the present invention is solved, there are no particular limitations on the components, conditions, values, etc.

[0010] "αβ amount (A / B)" means the β amount (α) of A relative to 100% by mass of B. α can be expressed, for example, in mass %, mol %, or parts by mass. β amount can be expressed, for example, in content or amount used. "% by mass content (A / B)" means the content (% by mass) of A relative to 100% by mass of B.

[0011] The term "γ ratio (A / B)" refers to the γ ratio calculated by the formula "A÷B." Examples of the γ ratio include a mass ratio and a molar ratio.

[0012] "Non-volatile content" refers to the total mass of components other than organic solvents and water. In one embodiment, "non-volatile content of A" refers to the total mass of components remaining when 1 g of A is heated at 105°C and reaches a constant weight.

[0013] "(Meth)acrylic" means "acrylic and / or methacrylic". "(Meth)acrylate" means "acrylate and / or methacrylate". "(Meth)acryloyl" means "acryloyl and / or methacryloyl".

[0014] Examples of the alkyl group include a linear alkyl group, a branched alkyl group, and a cycloalkyl group.

[0015] Examples of the straight-chain alkyl group include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, and an n-decyl group.

[0016] Examples of branched alkyl groups include an iso-propyl group, a sec-butyl group, an iso-butyl group, a tert-butyl group, a 2-ethylhexyl group, a diethylpentyl group, a trimethylbutyl group, a trimethylpentyl group, and a trimethylhexyl group.

[0017] Examples of the cycloalkyl group include a monocyclic cycloalkyl group, a bridged ring cycloalkyl group, a fused ring cycloalkyl group, etc. A cycloalkyl group in which at least one hydrogen atom of the cycloalkyl group is substituted with an alkyl group is also considered to be a cycloalkyl group.

[0018] "Monocyclic ring" means a ring structure formed by covalent carbon bonds and having no internal bridges. "Fused ring" means a ring structure in which two or more monocyclic rings share two atoms (i.e., each ring shares only one edge (fused) with another). "Bridged ring" means a ring structure in which two or more monocyclic rings share three or more atoms.

[0019] Examples of the monocyclic cycloalkyl group include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclodecyl group, and a 3,5,5-trimethylcyclohexyl group.

[0020] Examples of the bridged ring cycloalkyl group include a tricyclodecyl group, an adamantyl group, and a norbornyl group.

[0021] The alkyl group also includes a group formed by combining a linear alkyl group, a branched alkyl group, and a cycloalkyl group. Examples of the combined group include a cycloalkylalkyl group.

[0022] The cycloalkylalkyl group is represented by the following formula: R calkyl -R alkyl - (In the formula, R calkyl represents a cycloalkyl group. alkyl represents an alkyl group.

[0023] Examples of the alkylene group include a linear alkylene group, a branched alkylene group, and a cycloalkylene group.

[0024] Examples of the straight-chain alkylene group include a methylene group, an ethylene group, a propylene group, an n-butylene group, an n-pentylene group, an n-hexylene group, an n-heptylene group, an n-octylene group, an n-nonylene group, and an n-decamethylene group.

[0025] Examples of the branched alkylene group include a diethylpentylene group, a trimethylbutylene group, a trimethylpentylene group, and a trimethylhexylene group.

[0026] Examples of the cycloalkylene group include a monocyclic cycloalkylene group, a bridged ring cycloalkylene group, a fused ring cycloalkylene group, etc. In addition, one or more hydrogen atoms of the cycloalkylene group may be substituted with a linear or branched alkyl group.

[0027] Examples of the monocyclic cycloalkylene group include a cyclopentylene group, a cyclohexylene group, a cycloheptylene group, a cyclodecylene group, and a 3,5,5-trimethylcyclohexylene group.

[0028] Examples of the bridged ring cycloalkylene group include a tricyclodecylene group, an adamantylene group, and a norbornylene group.

[0029] Examples of the fused ring cycloalkylene group include a bicyclodecylene group.

[0030] The alkylene group also includes a group formed by combining a linear alkylene group, a branched alkylene group, and a cycloalkylene group, such as a cycloalkylene alkylene group and an alkylene cycloalkylene alkylene group.

[0031] The cycloalkylene alkylene group is represented by the following formula: -R calkylene -R alkylene - (In the formula, R calkylene represents a cycloalkylene group. alkylene represents an alkylene group.

[0032] The alkylenecycloalkylenealkylene group is represented by the following formula: -R alkylene -R calkylene -R alkylene - (In the formula, R calkylene represents a cycloalkylene group. alkylene represents an alkylene group.

[0033] The aromatic group (aryl group, arylene group) may be substituted or unsubstituted. Examples of the substituent of the aromatic group include an alkyl group, a thioalkyl group, a thioaryl group, and a carbonylaryl group.

[0034] Examples of the aryl group include a monocyclic aryl group and a fused ring aryl group.

[0035] Examples of the monocyclic aryl group include a phenyl group, a tolyl group, and a mesityl group.

[0036] The fused ring aryl group may, for example, be a naphthyl group.

[0037] Examples of the arylene group include a monocyclic arylene group and a fused ring arylene group.

[0038] Examples of the monocyclic arylene group include a phenylene group and a tolylene group.

[0039] The fused ring arylene group may, for example, be a naphthylene group.

[0040] [Coating agent] The present disclosure provides a coating agent, comprising: The coating agent includes a poly(meth)acrylate and a hyperbranched filler, The coating agent has a content of the multi-branched filler of 15% by mass to 90% by mass relative to 100% by mass of nonvolatile matter.

[0041] <Poly(meth)acrylate> The poly(meth)acrylates may be used alone or in combination of two or more.

[0042] "Poly(meth)acrylate" means a compound having two or more (meth)acryloyl groups.

[0043] Examples of poly(meth)acrylates include (poly)pentaerythritol poly(meth)acrylate, (poly)trimethylolpropane poly(meth)acrylate, (poly)glycerin poly(meth)acrylate, urethane poly(meth)acrylate, (meth)acryloyl group-containing (meth)acrylic polymer, double bond-containing silicone, and (meth)acryloyl group-containing perfluoropolyether.

[0044] (urethane poly(meth)acrylate) Examples of urethane poly(meth)acrylates include reaction products of a compound group containing a hydroxyl group-containing (poly)(meth)acrylate and a polyisocyanate.

[0045] <Hydroxyl group-containing poly(meth)acrylate> Examples of hydroxyl group-containing poly(meth)acrylates include hydroxyl group-containing (poly)pentaerythritol poly(meth)acrylate, hydroxyl group-containing (poly)trimethylolpropane poly(meth)acrylate, and hydroxyl group-containing (poly)glycerin poly(meth)acrylate.

[0046] The polyisocyanates may be used alone or in combination of two or more.

[0047] <Polyisocyanate> "Polyisocyanate" means a compound having two or more isocyanate groups (-N=C=O).

[0048] Examples of polyisocyanates include linear aliphatic polyisocyanates, branched aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic polyisocyanates, and biurets, isocyanurates, allophanates, adducts, and the like thereof.

[0049] Examples of the linear aliphatic polyisocyanate include methylene diisocyanate, dimethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, octamethylene diisocyanate, nonamethylene diisocyanate, and decamethylene diisocyanate.

[0050] Examples of branched aliphatic polyisocyanates include diethylpentylene diisocyanate, trimethylbutylene diisocyanate, trimethylpentylene diisocyanate, and trimethylhexamethylene diisocyanate.

[0051] Examples of the alicyclic polyisocyanate include monocyclic alicyclic polyisocyanates, crosslinked cyclic alicyclic polyisocyanates, and condensed cyclic alicyclic polyisocyanates.

[0052] Examples of monocyclic alicyclic polyisocyanates include hydrogenated xylene diisocyanate, isophorone diisocyanate, cyclopentylene diisocyanate, cyclohexylene diisocyanate, cycloheptylene diisocyanate, cyclodecylene diisocyanate, 3,5,5-trimethylcyclohexylene diisocyanate, and dicyclohexylmethane diisocyanate.

[0053] Examples of the crosslinked alicyclic polyisocyanate include tricyclodecylene diisocyanate, adamantane diisocyanate, and norbornene diisocyanate.

[0054] An example of the condensed ring alicyclic polyisocyanate is bicyclodecylene diisocyanate.

[0055] Examples of aromatic polyisocyanates include monocyclic aromatic polyisocyanates and condensed ring aromatic polyisocyanates.

[0056] Examples of the monocyclic aromatic polyisocyanate include dialkyldiphenylmethane diisocyanates such as 4,4'-diphenyldimethylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanates such as 4,4'-diphenyltetramethylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-dibenzyl isocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, and m-tetramethylxylylene diisocyanate.

[0057] The condensed ring aromatic polyisocyanate may, for example, be 1,5-naphthylene diisocyanate.

[0058] ((Meth)acryloyl group-containing (meth)acrylic polymer) The term "(meth)acryloyl group-containing (meth)acrylic polymer" refers to a polymer having two or more (meth)acryloyl groups.

[0059] <Double bond-containing site> Examples of the molar content (double bond-containing moiety / (meth)acryloyl group-containing (meth)acrylic polymer) include 50 mol%, 45 mol%, 40 mol%, 35 mol%, 30 mol%, 25 mol%, 20 mol%, 15 mol%, 10 mol%, and 5 mol%, etc. In one embodiment, the content is preferably 5 mol% to 50 mol%.

[0060] Examples of the mass % content (double bond-containing moiety / (meth)acryloyl group-containing (meth)acrylic polymer) include 50 mass %, 45 mass %, 40 mass %, 35 mass %, 30 mass %, 25 mass %, 20 mass %, 15 mass %, 10 mass %, 5 mass %, etc. In one embodiment, the content is preferably 5 mass % to 50 mass %.

[0061] <(Meth)acrylate Alkyl Unit> In one embodiment, the (meth)acryloyl group-containing (meth)acrylic polymer may contain alkyl (meth)acrylate units. The alkyl (meth)acrylate units may be contained alone or in combination of two or more.

[0062] Examples of the alkyl (meth)acrylate include linear alkyl (meth)acrylate, branched alkyl (meth)acrylate, and cycloalkyl (meth)acrylate.

[0063] Examples of linear alkyl (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, n-hexyl (meth)acrylate, n-heptyl (meth)acrylate, n-octyl (meth)acrylate, n-hexadecyl (meth)acrylate, n-dodecyl (meth)acrylate, n-octadecyl (meth)acrylate, n-icosyl (meth)acrylate, and n-docosyl (meth)acrylate.

[0064] Examples of branched alkyl (meth)acrylates include isopropyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate.

[0065] Examples of cycloalkyl (meth)acrylates include cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, cyclopentanyl (meth)acrylate, and isobornyl (meth)acrylate.

[0066] Examples of the molar content ((meth)acrylate alkyl units / (meth)acryloyl group-containing (meth)acrylic polymer) include 95 mol%, 90 mol%, 85 mol%, 80 mol%, 75 mol%, 70 mol%, 65 mol%, 60 mol%, 55 mol%, 50 mol%, 45 mol%, 40 mol%, 35 mol%, 30 mol%, 25 mol%, 20 mol%, 15 mol%, 10 mol%, 5 mol%, and 0 mol%. In one embodiment, the content is preferably 0 mol% to 95 mol%.

[0067] Examples of the mass % content ((meth)acrylate alkyl unit / (meth)acryloyl group-containing (meth)acrylic polymer) are 95 mass %, 90 mass %, 85 mass %, 80 mass %, 75 mass %, 70 mass %, 65 mass %, 60 mass %, 55 mass %, 50 mass %, 45 mass %, 40 mass %, 38 mass %, 35 mass %, 30 mass %, 25 mass %, 20 mass %, 15 mass %, 10 mass %, 5 mass %, 0 mass %, etc. In one embodiment, the content is preferably 0 mass % to 95 mass %.

[0068] <(Meth)acrylate Silicone Unit> In one embodiment, the (meth)acryloyl group-containing (meth)acrylic polymer may contain a (meth)acrylate silicone unit. The (meth)acrylate silicone unit may be contained alone or in combination of two or more types.

[0069] In one embodiment, the silicone (meth)acrylate is represented by the following formula: [ka] (In the formula, R AS1 , R AS2 each independently represents a hydrogen atom or a methyl group. AS1 represents an integer of 0 to 6. AS2 represents an integer of 1 to 270.

[0070] Examples of commercially available products ((meth)acrylate silicones) include X-22-2426 (manufactured by Shin-Etsu Silicones Co., Ltd.), X-22-174D (manufactured by Shin-Etsu Chemical Co., Ltd.), and Silaplane FM-0711, FM-0721, and FM-0725 (manufactured by JNC Corporation).

[0071] Examples of the molar content ((meth)acrylate silicone units / (meth)acryloyl group-containing (meth)acrylic polymer) are 50 mol%, 45 mol%, 40 mol%, 35 mol%, 30 mol%, 25 mol%, 20 mol%, 15 mol%, 10 mol%, 5 mol%, 0 mol%, etc. In one embodiment, the content is preferably 0 mol% to 50 mol%.

[0072] Examples of the mass % content ((meth)acrylate alkyl unit / (meth)acryloyl group-containing (meth)acrylic polymer) are 50 mass %, 45 mass %, 40 mass %, 35 mass %, 30 mass %, 25 mass %, 20 mass %, 15 mass %, 10 mass %, 5 mass %, 0 mass %, etc. In one embodiment, the content is preferably 0 mass % to 50 mass %.

[0073] <Perfluoroalkyl (meth)acrylate unit> In one embodiment, the (meth)acryloyl group-containing (meth)acrylic polymer may contain a (perfluoroalkyl (meth)acrylate unit. The perfluoroalkyl (meth)acrylate unit may be contained alone or in combination of two or more types.

[0074] In one embodiment, the perfluoroalkyl(meth)acrylate is represented by the following formula: CH2=C(CH3)-COO(CH2) f1 (CF2) f2 R f (R f represents a hydrogen atom or a fluorine atom. f1 represents 1 or 2. f2 represents an integer of 1 to 10.

[0075] Examples of the mole % content (perfluoroalkyl (meth)acrylate units / (meth)acryloyl group-containing (meth)acrylic polymer) are 50 mole %, 45 mole %, 40 mole %, 35 mole %, 30 mole %, 25 mole %, 20 mole %, 15 mole %, 10 mole %, 5 mole %, 0 mole %, etc. In one embodiment, the content is preferably 0 mole % to 50 mole %.

[0076] Examples of the mass % content (perfluoroalkyl (meth)acrylate units / (meth)acryloyl group-containing (meth)acrylic polymer) are 50 mass %, 45 mass %, 40 mass %, 35 mass %, 30 mass %, 25 mass %, 20 mass %, 15 mass %, 10 mass %, 5 mass %, 0 mass %, etc. In one embodiment, the content is preferably 0 mass % to 50 mass %.

[0077] <Production Method ((Meth)Acryloyl Group-Containing (Meth)Acrylic Polymer)> The production method (for the (meth)acryloyl group-containing (meth)acrylic polymer) may be, for example, a method of reacting an α-functional group-containing polymer with a β-functional group-containing polymerizable unsaturated compound.

[0078] Examples of combinations (of α functional groups and β functional groups) include the following. [Table A]

[0079] Examples of the carboxyl group-containing polymerizable unsaturated compound include (meth)acrylic acid and crotonic acid.

[0080] Examples of the epoxy group polymerizable unsaturated compound include glycidyl (meth)acrylate and β-methylglycidyl (meth)acrylate.

[0081] Examples of the hydroxyl group-containing polymerizable unsaturated compound include 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate.

[0082] Examples of the isocyanate group-containing polymerizable unsaturated compound include 2-isocyanatoethyl (meth)acrylate.

[0083] In one embodiment, the α-functional group-containing polymer is preferably a radical polymer.

[0084] In one embodiment, the production temperature (for the α-functional group-containing polymer) is preferably 80°C to 140°C.

[0085] Examples of the polymerization solvent (α-functional group-containing polymer) include toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl acetate, butyl acetate, cyclohexanone, ethylene dichloride, and carbon tetrachloride.

[0086] In one embodiment, the production temperature (for the (meth)acryloyl group-containing (meth)acrylic polymer) is preferably 80°C to 120°C.

[0087] Examples of the reaction solvent ((meth)acryloyl group-containing (meth)acrylic polymer) include methyl isobutyl ketone and butyl acetate.

[0088] (double bond-containing silicone) The double bond-containing silicones may be used alone or in combination of two or more.

[0089] In one embodiment, the double bond-containing silicone is represented by the formula: [ka] (In the formula, R S1 ~R S7 R each independently represents a methyl group or a group containing a polymerizable double bond. S8 ~R S11 R each independently represents a methyl group or a phenyl group. S12 represents a substituted methyl group or a substituted phenyl group. S1 represents an integer of 0 or more. S2 represents an integer of 1 or more. S3 represents an integer of 0 or more. However, the compound represented by the above formula has two or more polymerizable double bonds.

[0090] In one embodiment, the double bond-containing silicone is represented by the formula: [ka] (In the formula, R Sa1 ~R Sa3 R each independently represents a methyl group or a group containing a polymerizable double bond. Sa4 represents a substituted methyl group or a substituted phenyl group. S1 represents an integer of 0 or more. S2 represents an integer of 1 or more. S3 represents an integer of 0 or more. However, the compound represented by the above formula has two or more polymerizable double bonds.

[0091] Examples of the polymerizable double bond-containing group include a vinyl group-containing group, a (meth)acryloyl group-containing group, etc. Examples of the polymerizable double bond-containing group include a group in which the following substituent is combined with a vinyl group or a (meth)acryloyl group.

[0092] Examples of the substituent include an alkyl group, an alkylene group, an aryl group, an arylene group, an ether group, an ester group, a hydroxyl group, a keto group, and combinations of these groups.

[0093] In one embodiment, S1 is preferably an integer of 0 or more, and more preferably an integer of 0 to 10.

[0094] In one embodiment, S2 is preferably an integer of 1 or more, and more preferably an integer of 0 to 270.

[0095] In one embodiment, S3 is preferably an integer of 0 or more, and more preferably an integer of 0 to 5.

[0096] ((Meth)acryloyl group-containing perfluoropolyether) "(Meth)acryloyl group-containing perfluoropolyether" means a compound in which one or more (meth)acryloyl groups are bonded to a perfluoropolyether. "Perfluoropolyether" means a compound in which perfluoroalkylene ether is a repeating unit.

[0097] Examples of the (meth)acryloyl group-containing perfluoropolyether include perfluoropolyethers containing (meth)acryloyl groups at both ends and perfluoropolyethers containing a (meth)acryloyl group at one end.

[0098] Examples of the product ((meth)acryloyl group-containing perfluoropolyether) include KY-1211, KY-1203, KY-1207, and KY-1216 (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0099] In one embodiment, the (meth)acryloyl group-containing perfluoropolyether is preferably a silicon atom- and (meth)acryloyl group-containing perfluoropolyether. Examples of the product (silicon atom- and (meth)acryloyl group-containing perfluoropolyether) include KY-1203 (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0100] In one embodiment, the poly(meth)acrylate is preferably a silicone unit-containing poly(meth)acrylate or a perfluoroalkyl unit-containing poly(meth)acrylate, more preferably a (meth)acryloyl group-containing silicone acrylic polymer or a double bond-containing silicone, and even more preferably a (meth)acryloyl group-containing silicone acrylic polymer, a polyether-modified double bond-containing silicone, or a silicon atom and a (meth)acryloyl group-containing perfluoropolyether.

[0101] Examples of the mass % content (poly(meth)acrylate / coating agent nonvolatile content) include 85 mass %, 80 mass %, 75 mass %, 70 mass %, 65 mass %, 60 mass %, 55 mass %, 50 mass %, 45 mass %, 40 mass %, 35 mass %, 30 mass %, 25 mass %, 20 mass %, 15 mass %, 10 mass %, etc. In one embodiment, the content is preferably 10 mass % to 85 mass %.

[0102] <Hyperbranched filler> The hyperbranched fillers may be used alone or in combination of two or more.

[0103] Examples of the hyperbranched filler include hyperbranched inorganic fillers.

[0104] Examples of the hyperbranched inorganic filler include hyperbranched inorganic oxide fillers.

[0105] Examples of the hyperbranched inorganic oxide filler include hyperbranched zinc oxide filler, hyperbranched titanium oxide filler, and hyperbranched magnesium oxide filler.

[0106] Examples of the hyperbranched filler include a surface-untreated hyperbranched filler and a surface-treated hyperbranched filler.

[0107] Examples of the surface-treated hyperbranched filler include a hyperbranched filler treated with an aminosilane coupling agent, a hyperbranched filler treated with an epoxysilane coupling agent, and a hyperbranched filler treated with a titanate coupling agent.

[0108] The hyperbranched filler is composed of a core and branched portions extending from the core. Preferably, the hyperbranched filler has a core and branched portions extending from the core in four different axial directions. More preferably, the branched portions extend in the directions of the four vertices of a tetrahedron having the core as its center of gravity. Even more preferably, the tetrahedron is a regular tetrahedron.

[0109] The number of branches (hyperbranched filler) is, for example, 10, 9, 8, 7, 6, 5, 4, or 3. In one embodiment, the number of branches is preferably 3 to 10, more preferably 3 to 5, and even more preferably 4.

[0110] The average fiber length (branch portion) is, for example, 50 μm, 45 μm, 40 μm, 35 μm, 30 μm, 25 μm, 20 μm, 15 μm, 10 μm, 5 μm, 2 μm, 1 μm, etc. In one embodiment, the average fiber length is preferably 1 μm to 50 μm, more preferably 2 μm to 50 μm, and even more preferably 5 μm to 15 μm.

[0111] Examples of the average fiber diameter (branch portion) include 15 μm, 10 μm, 5 μm, 3 μm, 2 μm, 1 μm, 0.5 μm, 0.3 μm, and 0.2 μm. In one embodiment, the average fiber diameter is preferably 0.2 μm to 15 μm, and more preferably 0.2 μm to 3 μm.

[0112] The average fiber length and average fiber diameter can be measured by the following procedure. (1) Disperse the hyperbranched filler in a solvent such as alcohol. (2) Using an electron microscope, measure the fiber length and diameter of 100 fibers. (3) Calculate the average of the 100 measured values.

[0113] Examples of the shape (branch) include a cone shape and a pyramid shape.

[0114] Examples of the product (hyperbranched filler) include Pana-Tetra WZ-0501, WZ-0501L, WZ-0511, WZ-0511L, WZ-0531, WZ-05E1, and WZ-05F1 (all hyperbranched zinc oxide fillers, manufactured by Amtec Corporation); FTL-100, FTL-110, FTL-200, and FTL-300 (all hyperbranched titanium oxide fillers, manufactured by Ishihara Sangyo Kaisha, Ltd.); and TOFIX-P (hyperbranched titanium oxide filler, manufactured by Toho Titanium Co., Ltd.).

[0115] Examples of the mass % content (hyperbranched filler / nonvolatile content of coating agent) include 90 mass %, 85 mass %, 80 mass %, 75 mass %, 70 mass %, 65 mass %, 60 mass %, 55 mass %, 50 mass %, 45 mass %, 40 mass %, 35 mass %, 30 mass %, 25 mass %, 20 mass %, 15 mass %, etc. In one embodiment, the content is preferably 15 mass % to 90 mass %. <Photopolymerization initiator> In one embodiment, the active energy ray-curable composition may optionally contain a photopolymerization initiator. The photopolymerization initiators may be used alone or in combination of two or more.

[0116] Examples of the photopolymerization initiator include an α-hydroxydimethylacetophenone group-containing photopolymerization initiator, α-hydroxycycloalkylphenone, α-aminoalkylphenone, benzyl dimethyl ketal, unsubstituted or substituted alkylphenone, unsubstituted or substituted benzyl, unsubstituted or substituted benzophenone, acylphosphine oxide, substituted thioxanthone, and oxime ester.

[0117] Examples of the α-hydroxydimethylacetophenone group-containing photopolymerization initiator include 2-hydroxy-2-methyl-1-phenylpropanone, 1-[4-(2-hydroxyethoxyl)-phenyl]-2-hydroxy-methylpropanone, and 2-hydroxy-1-(4-(4-(2-hydroxy-2-methylpropionyl)benzyl)phenyl)-2-methylpropan-1-one.

[0118] Examples of α-hydroxycycloalkylphenones include 1-hydroxycyclohexyl phenyl ketone.

[0119] Examples of α-aminoalkylphenones include 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one.

[0120] Examples of benzyl dimethyl ketals include 2,2-dimethoxy-1,2-diphenylethan-1-one.

[0121] Examples of unsubstituted or substituted alkylphenones include benzoin methyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin ethyl ether, acetophenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2-phenyl-2-(p-toluenesulfonyloxy)acetophenone, benzoin, 2-benzyl-2-(dimethylamino)-4'-morpholinobutyrophenone, 2-methyl-4'-(methylthio)-2-morpholinopropiophenone, 2-isonitrosopropiophenone, and 2,2-dimethoxy-1,2-diphenylethan-1-one.

[0122] Examples of unsubstituted or substituted benzyl include benzyl and p-anisyl.

[0123] Examples of unsubstituted or substituted benzophenones include benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-dichlorobenzophenone, 1,4-dibenzoylbenzene, 2-benzoylbenzoic acid, 4-benzoylbenzoic acid, and methyl 2-benzoylbenzoate.

[0124] Examples of the acylphosphine oxide include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide.

[0125] Examples of substituted thioxanthone include 2-chlorothioxanthone, 2-isopropylthioxanthone, and 2,4-diethylthioxanthone.

[0126] Oxime esters include, for example, 1,2-octanedione, 1-[4-(phenylthio)-, 2-(O-benzoyloxime)] (i.e., 2-((benzoyloxy)imino)-1-(4-(phenylthio)phenyl)octan-1-one); Examples include ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime) (i.e., 1-(((1-(9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl)ethylidene)amino)oxy)ethan-1-one).

[0127] When electron beam curing is used, a photoinitiator is not required.

[0128] Examples of the mass % content (photopolymerization initiator / active energy ray-curable composition nonvolatile content) include 10 mass %, 9 mass %, 8 mass %, 7 mass %, 6 mass %, 5 mass %, 4 mass %, 3 mass %, 2 mass %, 1 mass %, 0 mass %, etc. In one embodiment, the content is preferably 0 mass % to 10 mass %, and more preferably 1 mass % to 6 mass %.

[0129] <Organic solvents> In one embodiment, the active energy ray-curable composition may optionally contain an organic solvent. The organic solvent may be used alone or in combination of two or more kinds.

[0130] Examples of the organic solvent include ketone solvents, aromatic solvents, alcohol solvents, glycol solvents, glycol ether solvents, ester solvents, petroleum-based solvents, haloalkane solvents, and amide solvents.

[0131] Examples of the ketone solvent include methyl ethyl ketone, acetylacetone, methyl isobutyl ketone, cyclopentanone, and cyclohexanone.

[0132] Examples of aromatic solvents include toluene and xylene.

[0133] Examples of the alcohol solvent include methanol, ethanol, n-propanol, isopropanol, n-butanol, i-butanol, and t-butanol.

[0134] Examples of glycol solvents include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, polyethylene glycol, and polypropylene glycol.

[0135] Examples of glycol ether solvents include ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol monoisopropyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol monoisobutyl ether, and ethylene glycol mono-t-butyl ether.

[0136] Examples of the ester solvent include ethyl acetate, butyl acetate, methyl cellosolve acetate, ethyl cellosolve acetate, and propylene glycol monomethyl ether acetate.

[0137] Examples of petroleum-based solvents include Solvesso #100 (manufactured by Exxon Chemical), Solvesso #150 (manufactured by Exxon Chemical), and the like.

[0138] Examples of haloalkane solvents include chloroform.

[0139] The amide solvent may, for example, be dimethylformamide.

[0140] In one embodiment, the organic solvent is preferably an alcohol solvent or a glycol ether solvent, more preferably isopropyl alcohol, n-butanol, isobutanol, or propylene glycol monomethyl ether, even more preferably a combination of isopropyl alcohol and propylene glycol monomethyl ether, or a combination of isopropyl alcohol and propylene glycol monomethyl ether, and particularly preferably a combination of isopropyl alcohol and propylene glycol monomethyl ether. The reason for this preference is, for example, improvement in leveling properties.

[0141] Examples of the mass % content (organic solvent / active energy ray-curable composition) include 99 mass %, 98.5 mass %, 98 mass %, 97 mass %, 95 mass %, 90 mass %, 85 mass %, 80 mass %, 75 mass %, 70 mass %, 65 mass %, 60 mass %, 55 mass %, 50 mass %, 45 mass %, 40 mass %, 35 mass %, 30 mass %, 25 mass %, 20 mass %, 15 mass %, 10 mass %, 5 mass %, and 0 mass %. In one embodiment, the content is preferably 0 mass % to 99 mass %. <Additives> The coating agent may optionally contain an agent (additive) that does not fall into any of the above categories.

[0142] Examples of additives include weather resistance stabilizers, heat resistance stabilizers, silicone oils, antislip agents, antistatic agents, antiblocking agents, antifogging agents, lubricants, dyes, plasticizers, antioxidants, hydrochloric acid absorbers, antioxidants, crystal nucleating agents, antibacterial agents, flame retardants, organic fillers, inorganic fillers, ultraviolet absorbers, infrared absorbers, antifoaming agents, surface conditioners, antifouling agents, and pigments.

[0143] In one embodiment, the content in parts by mass (additive / coating agent) is preferably less than 1 part by mass, less than 0.1 part by mass, less than 0.01 part by mass, 0 part by mass, or the like.

[0144] In one embodiment, the parts by mass content (additive / poly(meth)acrylate), the parts by mass content (additive / multi-branched filler), the parts by mass content (additive / photopolymerization initiator), and the parts by mass content (additive / organic solvent) are preferably less than 1 part by mass, less than 0.1 parts by mass, less than 0.01 parts by mass, 0 parts by mass, etc., respectively.

[0145] The coating agent can be produced by dispersing and mixing the above agents.

[0146] Examples of the dispersing and mixing means include an emulsifying disperser and an ultrasonic dispersing device.

[0147] Examples of applications (coating agents) include water-repellent coating agents and antibacterial coating agents.

[0148] [Cured product] The present disclosure relates to a cured product of the above coating agent.

[0149] Examples of the curing conditions include the following conditions.

[0150] [Laminate] The present disclosure relates to a laminate comprising the above-mentioned cured product.

[0151] The manufacturing method (laminate) may include, for example, a method including the following steps. Active energy ray curable composition coating step: a step of coating an active energy ray curable composition on at least one surface of a substrate. Active energy ray curing step: a step of irradiating active energy rays to form a cured layer of the active energy ray curable composition.

[0152] Examples of the substrate include polyethylene terephthalate (PET), polycarbonate film, acrylic film (such as polymethyl methacrylate film), polystyrene film, polyester film, polyolefin film, epoxy resin film, melamine resin film, triacetyl cellulose film, ABS film, AS film, norbornene resin film, polyamide film, polyimide film, cyclic olefin film, polyvinyl alcohol film, metal, wood, paper, glass, and slate.

[0153] In one embodiment, the thickness (substrate) is preferably 10 μm to 2000 μm.

[0154] In one embodiment, the thickness (of the cured product layer) is preferably 0.05 μm to 20 μm.

[0155] (Coating process) Examples of the coating method include bar coater coating, applicator coating, roll coating, wire bar coating, knife coating, Mayer bar coating, spray coating, comma coating, dip coating, air knife coating, gravure coating, reverse gravure coating, flow coat coating, offset printing, flexographic printing, and screen printing.

[0156] (Active energy ray curing process) Examples of the active energy ray include ultraviolet rays and electron beams.

[0157] Examples of ultraviolet light sources include xenon lamps, low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, carbon arc lamps, metal halide lamps, chemical lamps, electrodeless lamps, LED lamps, and electron beam irradiation devices.

[0158] When a high-pressure mercury lamp is used, the curing conditions are preferably the following conditions. Lamp output: 25W / cm~160W / cm UV illuminance: 10mW / cm 2~800mW / cm 2 Accumulated light output: 25mJ / cm 2 ~5000mJ / cm 2 Conveying speed: 1m / min to 50m / min

[0159] When electron beams are used, the curing conditions are preferably the following conditions. Acceleration voltage: 10 kV to 300 kV Conveying speed: 5m / min to 50m / min [Example]

[0160] The present invention will be described in detail below through examples and comparative examples. However, the above description and the following examples are not intended to limit the present invention. The present invention is limited only by the claims. Unless otherwise specified below, numerical values ​​such as parts and % are based on mass.

[0161] Manufacturing Example 1 A four-neck flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen inlet was charged with 125 parts of butyl acetate, 100 parts of glycidyl methacrylate (GMA), and 1 part of azobisisobutyronitrile (AIBN), and the mixture was stirred and heated to 100 ° C under a nitrogen stream. After the reaction was completed, the mixture was cooled to 60 ° C, and 25 parts of acrylic acid (AA), 0.1 parts of triphenylphosphine, and 0.05 parts of methoquinone were added. The nitrogen inlet was replaced with an air bubbling device, and the mixture was stirred while bubbling air into the reaction solution. The mixture was heated to 110 ° C and allowed to react for 9 hours, resulting in a (meth)acryloyl group-containing (meth)acrylic polymer (non-volatile content 50%).

[0162] Manufacturing Example 2 A reaction vessel equipped with a thermometer, a stirrer, a condenser, a dropping funnel, and a nitrogen inlet tube was charged with 200 g of an isocyanurate of isophorone diisocyanate, 0.2 g of tin octylate, and 268 g of pentaerythritol triacrylate, and the temperature in the system was then raised to about 80°C over about 1 hour. The reaction system was then maintained at the same temperature for 3 hours, and the reaction mixture was heated to 2250 cm3, which represents the isocyanate group.-1 The reaction was continued until the infrared absorption spectrum of the compound disappeared, yielding a urethane polyacrylate with a double bond equivalent of 173 g / eq and a weight-average molecular weight of 1,560.

[0163] Example The substances listed in the table below were mixed as nonvolatile components and then diluted (dilution solvent: propylene glycol monomethyl ether, nonvolatile content: 30%).

[0164] [Table 1] 8SS-723: (Meth)acryloyl group-containing silicone acrylic polymer, manufactured by Taisei Fine Chemical Co., Ltd. Tegorad2200N: Polyether-modified double bond-containing silicone, manufactured by Evonik KY-1203: (meth)acryloyl group-containing perfluoropolyether, manufactured by Shin-Etsu Chemical Co., Ltd. WZ-0501: Product name "Panatetra WZ-0501", untreated tetrahedral zinc oxide filler, average fiber length (branch) = 10 μm, manufactured by Amtec Co., Ltd. Omnirad 184: 1-hydroxycyclohexyl phenyl ketone, IGM Resins

[0165] (laminate) The coating agent was applied to the substrate using a bar coater so that the film thickness after drying would be 10 μm, and after drying at 80°C for 1 minute, it was irradiated with a high-pressure mercury lamp (300 mJ / cm 2 ) to obtain a laminate. Base material: Cosmoshine 100A4160 (polyester film, manufactured by Toyobo Co., Ltd.)

[0166] (Initial water repellency) The laminate was fixed to a glass plate with the coating surface facing upward, and after neutralization, a 2 μL droplet of deionized water was gently attached using a Kyowa Interface Science Co., Ltd. contact angle meter, "DropMaster DM500," and the contact angle was measured after 1 second (analysis method: θ / 2 method). If the static contact angle exceeds 150°, the liquid can no longer stand on the substrate surface. In this case, the result was recorded as "unmeasurable." "Unmeasurable" means that the water repellency is very good.

[0167] Evaluation example 1: Water repellency after steel wool test The laminate was placed in a steel wool tester with the coated surface facing upwards, and 1 kg / 1 cm was applied using #0000 steel wool. 2 The steel wool test was carried out by rubbing the test piece back and forth 10 times with a sliding distance of 4 cm under a load of 10. After the steel wool test, the water contact angle of the test piece was measured by the same method as above.

[0168] [Table 2]

[0169] Evaluation example 2: Antibacterial test The laminate was subjected to an antibacterial test in accordance with JIS Z2801, and the test results are shown in Table 3. In this study, only Staphylococcus aureus testing was performed.

[0170] [Table 3] *Antibacterial activity values ​​were calculated using Comparative Evaluation Example 2-1 as the blank.

[0171] The laminate of Evaluation Example 2-1 had an antibacterial activity value of 2.0 or more (a mortality rate of 99% or more), which indicates that the cured coating material of the present invention has excellent antibacterial properties (antibacterial properties).

Claims

1. A coating agent, The coating agent comprises a poly(meth)acrylate and a hyperbranched filler, The coating agent has a content of the hyperbranched filler of 15% by mass to 90% by mass relative to 100% by mass of nonvolatile matter.

2. The coating agent according to claim 1 , wherein the poly(meth)acrylate comprises silicone units and / or perfluoroalkyl units.

3. A cured product of the coating agent according to claim 1 or 2.

4. A laminate comprising the cured product according to claim 3.

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