Active energy ray-curable composition, cured product, and laminate

Abstract

To provide an active energy ray-curable composition, a cured product, and a laminate.SOLUTION: Provided is an active energy ray-curable composition, wherein the active energy ray-curable composition comprises poly(meth)acrylate, particles, and a phosphate ester.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present disclosure relates to an active energy ray-curable composition, a cured product, and a laminate. [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] An object of the present invention is to provide an active energy ray-curable composition which can produce a cured product having good scratch resistance. [Means for solving the problem]

[0005] The present disclosure provides the following: (Item 1) An active energy ray-curable composition, The active energy ray-curable composition includes poly(meth)acrylate, particles, and a phosphoric acid ester. (Item 2) The active energy ray-curable composition according to the above item, containing 0.1% by mass to 10% by mass of a phosphoric acid ester relative to 100% by mass of the nonvolatile content of the active energy ray-curable composition. (Item 3) A cured product of the active energy ray-curable composition according to any one of the above items. (Item 4) A laminate comprising the cured product described above.

[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. Effect of the Invention

[0007] The cured product of the present invention exhibits good scratch resistance. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[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 A2 or less), 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 ...2, greater than A2 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, and the like.

[0009] As long as the problem to be solved by the present invention is solved, the components, conditions, values, etc. are not particularly limited.

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

[0011] "γ ratio (A / B)" means a 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 1.5 g of A is heated at 150°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 straight-chain 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 the branched alkyl group include an i-propyl 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 condensed ring cycloalkyl group, etc. A cycloalkyl group in which at least one hydrogen atom 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 with no internal bridges. "Fused ring" means a ring structure in which two or more monocyclic rings share two atoms in common (i.e., each ring shares only one edge with the other (fused)). "Bridged ring" means a ring structure in which two or more monocyclic rings share three or more atoms in common.

[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 R represents a cycloalkyl group. alkyl represents an alkyl group.

[0023] Examples of the alkylene group include a straight-chain 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 condensed ring cycloalkylene group, etc. In addition, the cycloalkylene group may have one or more hydrogen atoms substituted with a straight-chain 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, an alkylenecycloalkylene alkylene group, and the like.

[0031] The cycloalkylene alkylene group is represented by the following formula: -R calkylene -R alkylene - (In the formula, R calkylene R 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 R 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 condensed 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] [Active energy ray-curable composition: composition] The present disclosure relates to an active energy ray-curable composition, the active energy ray-curable composition comprising a poly(meth)acrylate, particles, and a phosphate ester.

[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] The number of (meth)acryloyl groups (poly(meth)acrylate) is, for example, 20, 19, 18, 17, 16, 15, 14, 13, 12, 11, 10, 9, 8, 7, 6, 5, 4, 3, or 2. In one embodiment, the number of (meth)acryloyl groups is preferably 2 to 20.

[0044] Examples of the poly(meth)acrylate include poly(meth)acrylate containing no urethane bond, urethane poly(meth)acrylate, and carboxyl group-containing poly(meth)acrylate.

[0045] (Poly(meth)acrylate not containing urethane bonds) Examples of the urethane bond-free poly(meth)acrylate include (poly)pentaerythritol poly(alkylene oxide-modified or epoxy-modified) (meth)acrylate, (poly)trimethylolpropane poly(alkylene oxide-modified or epoxy-modified) (meth)acrylate, (poly)glycerin poly(alkylene oxide-modified or epoxy-modified) (meth)acrylate, isocyanurate structure-containing poly(alkylene oxide-modified or epoxy-modified) (meth)acrylate, (poly)alkylene di(alkylene oxide-modified or epoxy-modified) (meth)acrylate, and bisphenol A di(alkylene oxide-modified or epoxy-modified) (meth)acrylate.

[0046] "Poly(alkylene oxide-modified or epoxy-modified) (meth)acrylate" means one or more selected from the group consisting of poly(meth)acrylate, polyalkylene oxide-modified (meth)acrylate, and polyepoxy-modified (meth)acrylate.

[0047] <(Poly)pentaerythritol poly(alkylene oxide-modified or epoxy-modified) (meth)acrylate> (Poly)pentaerythritol poly(alkylene oxide-modified or epoxy-modified) (meth)acrylate is a compound represented by formula (A') or the like. [ka] [In the formula, n is an integer of 0 to 2, and R b1’ ~R b6 ’ each independently represents a hydrogen atom, [ka] In the formula, each q is independently an integer of 0 to 16; 1’ ~R 3’ are each independently a hydrogen atom or an alkyl group, R 1’may be different groups for each unit. and R b4’ and R b5’ may be different groups for each structural unit, Formula (A ’ ) in [ka] In the formula, q is an integer of 0 to 16, and R 1’ ~R 3 ’ are each independently a hydrogen atom or an alkyl group, R 1’ may be different groups for each unit. Contains two or more.

[0048] In addition, the phrase "the groups may be different for each structural unit" means that, for example, in formula (A'), when n is 2, [ka] R b4A and R b4B may be a group different from R b5A and R b5B This means that the group may be different from the group.

[0049] Examples of the pentaerythritol poly(meth)acrylate include pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, and pentaerythritol tetra(meth)acrylate.

[0050] Examples of pentaerythritol polyalkylene oxide-modified (meth)acrylates include pentaerythritol di(ethylene oxide-modified (meth)acrylate), pentaerythritol tri(ethylene oxide-modified (meth)acrylate), pentaerythritol tetra(ethylene oxide-modified (meth)acrylate), pentaerythritol di(propylene oxide-modified (meth)acrylate), pentaerythritol tri(propylene oxide-modified (meth)acrylate), and pentaerythritol tetra(propylene oxide-modified (meth)acrylate).

[0051] Examples of the pentaerythritol polyepoxy modified (meth)acrylate include pentaerythritol diepoxy (meth)acrylate, pentaerythritol triepoxy (meth)acrylate, and pentaerythritol tetraepoxy (meth)acrylate.

[0052] Examples of polypentaerythritol poly(meth)acrylates include dipentaerythritol di(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol di(meth)acrylate, tripentaerythritol tri(meth)acrylate, tripentaerythritol tetra(meth)acrylate, tripentaerythritol penta(meth)acrylate, tripentaerythritol hexa(meth)acrylate, tripentaerythritol hepta(meth)acrylate, and tripentaerythritol octa(meth)acrylate.

[0053] Examples of polypentaerythritol polyalkylene oxide modified (meth)acrylates include dipentaerythritol di(ethylene oxide modified (meth)acrylate), dipentaerythritol tri(ethylene oxide modified (meth)acrylate), dipentaerythritol tetra(ethylene oxide modified (meth)acrylate), dipentaerythritol penta(ethylene oxide modified (meth)acrylate), dipentaerythritol hexa(ethylene oxide modified (meth)acrylate), dipentaerythritol di(propionate), propylene oxide modified (meth)acrylate), dipentaerythritol tri(propylene oxide modified (meth)acrylate), dipentaerythritol tetra(propylene oxide modified (meth)acrylate), dipentaerythritol penta(propylene oxide modified (meth)acrylate), dipentaerythritol hexa(propylene oxide modified (meth)acrylate), tripentaerythritol di(ethylene oxide modified (meth)acrylate), tripentaerythritol tri(ethylene oxide modified (meth )acrylate), tripentaerythritol tetra(ethylene oxide modified (meth)acrylate), tripentaerythritol penta(ethylene oxide modified (meth)acrylate), tripentaerythritol hexa(ethylene oxide modified (meth)acrylate), tripentaerythritol hepta(ethylene oxide modified (meth)acrylate), tripentaerythritol octa(ethylene oxide modified (meth)acrylate), tripentaerythritol di(propylene oxide modified (meth)acrylate), tripentaerythritol tetra(ethylene oxide modified (meth)acrylate), tripentaerythritol penta(ethylene oxide modified (meth)acrylate), tripentaerythritol hexa(ethylene oxide modified (meth)acrylate), tripentaerythritol hepta(ethylene oxide modified (meth)acrylate), tripentaerythritol octa(ethylene oxide modified (meth)acrylate), tripentaerythritol di(propylene oxide modified (meth)acrylate), tripentaerythritol hexa ... Examples of the monomer include pentaerythritol tri(propylene oxide modified (meth)acrylate), tripentaerythritol tetra(propylene oxide modified (meth)acrylate), tripentaerythritol penta(propylene oxide modified (meth)acrylate), tripentaerythritol hexa(propylene oxide modified (meth)acrylate), tripentaerythritol hepta(propylene oxide modified (meth)acrylate), and tripentaerythritol octa(propylene oxide modified (meth)acrylate).

[0054] Examples of polypentaerythritol polyepoxy modified (meth)acrylates include dipentaerythritol diepoxy (meth)acrylate, dipentaerythritol triepoxy (meth)acrylate, dipentaerythritol tetraepoxy (meth)acrylate, dipentaerythritol pentaepoxy (meth)acrylate, dipentaerythritol hexapoxy (meth)acrylate, tripentaerythritol diepoxy (meth)acrylate, tripentaerythritol triepoxy (meth)acrylate, tripentaerythritol tetraepoxy (meth)acrylate, tripentaerythritol pentaepoxy (meth)acrylate, tripentaerythritol hexapoxy (meth)acrylate, tripentaerythritol heptaepoxy (meth)acrylate, and tripentaerythritol octaepoxy (meth)acrylate.

[0055] <(Poly)trimethylolpropane poly(alkylene oxide modified or epoxy modified) (meth)acrylate> (Poly)trimethylolpropane poly(alkylene oxide-modified or epoxy-modified) (meth)acrylate is a compound represented by formula (B') or the like. [ka] [In the formula, m is an integer of 0 to 2, and R b7’ ~R b10 ’ each independently represents a hydrogen atom, [ka] In the formula, each q is independently an integer of 0 to 16; 1’ ~R 3’ are each independently a hydrogen atom or an alkyl group, R 1’ may be different groups for each unit. and R b9’ may be different groups for each structural unit, Formula (B ’ ) in [ka] In the formula, q is an integer of 0 to 16, and R 1’ ~R 3 ’ are each independently a hydrogen atom or an alkyl group, R 1’ may be different groups for each unit. Contains two or more.

[0056] Examples of trimethylolpropane poly(meth)acrylate include trimethylolpropane di(meth)acrylate and trimethylolpropane tri(meth)acrylate.

[0057] Examples of trimethylolpropane polyalkylene oxide-modified (meth)acrylates include trimethylolpropane di(ethylene oxide-modified (meth)acrylate), trimethylolpropane tri(ethylene oxide-modified (meth)acrylate), trimethylolpropane di(propylene oxide-modified (meth)acrylate), and trimethylolpropane tri(propylene oxide-modified (meth)acrylate).

[0058] Examples of trimethylolpropane polyepoxy modified (meth)acrylates include trimethylolpropane diepoxy (meth)acrylate and trimethylolpropane triepoxy (meth)acrylate.

[0059] Examples of polytrimethylolpropane poly(meth)acrylates include ditrimethylolpropane di(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, and ditrimethylolpropane tetra(meth)acrylate.

[0060] Examples of polytrimethylolpropane polyalkylene oxide-modified (meth)acrylates include ditrimethylolpropane di(ethylene oxide-modified (meth)acrylate), ditrimethylolpropane tri(ethylene oxide-modified (meth)acrylate), ditrimethylolpropane tetra(ethylene oxide-modified (meth)acrylate), ditrimethylolpropane di(propylene oxide-modified (meth)acrylate), ditrimethylolpropane tri(propylene oxide-modified (meth)acrylate), and ditrimethylolpropane tetra(propylene oxide-modified (meth)acrylate).

[0061] Examples of polytrimethylolpropane polyepoxy modified (meth)acrylates include ditrimethylolpropane diepoxy (meth)acrylate, ditrimethylolpropane triepoxy (meth)acrylate, and ditrimethylolpropane tetraepoxy (meth)acrylate.

[0062] <(Poly)glycerin poly(alkylene oxide modified or epoxy modified) (meth)acrylate> The (poly)glycerin poly(alkylene oxide-modified or epoxy-modified) (meth)acrylate is a compound represented by formula (C') or the like. [ka] [In the formula, p is an integer of 0 to 7, and R b11’ ~R b14 ’ each independently represents a hydrogen atom, [ka] In the formula, q is an integer of 0 to 16, and R 1’ ~R 3’ are each independently a hydrogen atom or an alkyl group, R 1’ may be different groups for each unit. and R b13’ may be different groups for each structural unit, Formula (C ’) in [ka] In the formula, q is an integer of 0 to 16, and R 1’ ~R 3 ’ are each independently a hydrogen atom or an alkyl group, R 1’ may be different groups for each unit. Contains two or more.

[0063] Examples of the glycerin poly(meth)acrylate include glycerin di(meth)acrylate and glycerin tri(meth)acrylate.

[0064] Examples of the glycerin polyalkylene oxide-modified (meth)acrylate include glycerin di(ethylene oxide-modified (meth)acrylate), glycerin tri(ethylene oxide-modified (meth)acrylate), glycerin di(propylene oxide-modified (meth)acrylate), and glycerin tri(propylene oxide-modified (meth)acrylate).

[0065] Examples of the glycerin polyepoxy modified (meth)acrylate include glycerin diepoxy (meth)acrylate and glycerin triepoxy (meth)acrylate.

[0066] Examples of polyglycerol poly(meth)acrylates include diglycerol di(meth)acrylate, diglycerol tri(meth)acrylate, diglycerol tetra(meth)acrylate, triglycerol di(meth)acrylate, triglycerol tri(meth)acrylate, triglycerol tetra(meth)acrylate, and triglycerol penta(meth)acrylate.

[0067] Examples of polyglycerol polyalkylene oxide-modified (meth)acrylates include diglycerol di(ethylene oxide-modified (meth)acrylate), diglycerol tri(ethylene oxide-modified (meth)acrylate), diglycerol tetra(ethylene oxide-modified (meth)acrylate), triglycerol di(ethylene oxide-modified (meth)acrylate), triglycerol tri(ethylene oxide-modified (meth)acrylate), triglycerol tetra(ethylene oxide-modified (meth)acrylate), triglycerol penta(ethylene oxide-modified (Meth)acrylate) diglycerin di(propylene oxide modified (meth)acrylate), diglycerin tri(propylene oxide modified (meth)acrylate), diglycerin tetra(propylene oxide modified (meth)acrylate), triglycerin di(propylene oxide modified (meth)acrylate), triglycerin tri(propylene oxide modified (meth)acrylate), triglycerin tetra(propylene oxide modified (meth)acrylate), triglycerin penta(propylene oxide modified (meth)acrylate), and the like.

[0068] Examples of polyglycerol polyepoxy modified (meth)acrylates include diglycerol diepoxy (meth)acrylate, diglycerol triepoxy (meth)acrylate, diglycerol tetraepoxy (meth)acrylate, triglycerol diepoxy (meth)acrylate, triglycerol triepoxy (meth)acrylate, triglycerol tetraepoxy (meth)acrylate, and triglycerol pentaepoxy (meth)acrylate.

[0069] <Isocyanurate structure-containing poly(alkylene oxide-modified or epoxy-modified) (meth)acrylate> The isocyanurate structure-containing poly(alkylene oxide-modified or epoxy-modified) (meth)acrylate is a compound represented by formula (D') or the like. [ka] [In the formula, R b15’~R b17 ’ each independently represents a hydrogen atom, [ka] In the formula, q is an integer of 0 to 16, and R 1’ ~R 3’ are each independently a hydrogen atom or an alkyl group, R 1’ may be different groups for each unit. and the formula (D ’ ) in [ka] In the formula, q is an integer of 0 to 16, and R 1’ ~R 3 ’ are each independently a hydrogen atom or an alkyl group, R 1’ may be different groups for each unit. Contains two or more.

[0070] Examples of the isocyanurate structure-containing poly(meth)acrylate include isocyanuric acid di(meth)acrylate and isocyanuric acid tri(meth)acrylate.

[0071] Examples of the isocyanurate structure-containing polyalkylene oxide-modified (meth)acrylate include isocyanuric acid di(ethylene oxide-modified (meth)acrylate) and isocyanuric acid tri(ethylene oxide-modified (meth)acrylate).

[0072] Examples of the isocyanurate structure-containing polyepoxy-modified (meth)acrylate include isocyanuric acid diepoxy-modified (meth)acrylate and isocyanuric acid triepoxy-modified (meth)acrylate.

[0073] <(Poly)alkylene di(alkylene oxide modified or epoxy modified)(meth)acrylate> The (poly)alkylene di(alkylene oxide-modified or epoxy-modified)(meth)acrylate is a compound represented by the formula (E') or the like. [ka] [In the formula, R b18’ ~R b19 ’ are each independently [ka] In the formula, q is an integer of 0 to 16, and R 1’ ~R 3 ’ are each independently a hydrogen atom or an alkyl group, R 1’ may be different groups for each unit. and R b20’ is an alkylene group, and r is an integer of 1 or more.

[0074] Examples of the alkylene di(meth)acrylate include 1,2-ethylenediol di(meth)acrylate, 1,3-propanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,5-pentanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,7-heptanediol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, and neopentyl glycol di(meth)acrylate.

[0075] Examples of the alkylene dialkylene oxide modified (meth)acrylate include 1,2-ethylenediol di(ethylene oxide modified (meth)acrylate), 1,3-propanediol di(ethylene oxide modified (meth)acrylate), 1,4-butanediol di(ethylene oxide modified (meth)acrylate), 1,5-pentanediol di(ethylene oxide modified (meth)acrylate), 1,6-hexanediol di(ethylene oxide modified (meth)acrylate), 1,7-heptanediol di(ethylene oxide modified (meth)acrylate), 1,8-octanediol di(ethylene oxide modified (meth)acrylate), 1,9-nonanediol di(ethylene oxide modified (meth)acrylate), 1,10-decanediol di(ethylene oxide modified (meth)acrylate), neopentyl glycol di(ethylene oxide modified (meth)acrylate), ) acrylate), 1,2-ethylenediol di(propylene oxide modified (meth)acrylate), 1,3-propanediol di(propylene oxide modified (meth)acrylate), 1,4-butanediol di(propylene oxide modified (meth)acrylate), 1,5-pentanediol di(propylene oxide modified (meth)acrylate), 1,6-hexanediol di(propylene oxide modified (meth)acrylate ), 1,7-heptanediol di(propylene oxide modified (meth)acrylate), 1,8-octanediol di(propylene oxide modified (meth)acrylate), 1,9-nonanediol di(propylene oxide modified (meth)acrylate), 1,10-decanediol di(propylene oxide modified (meth)acrylate), neopentyl glycol di(propylene oxide modified (meth)acrylate), and the like.

[0076] Examples of the alkylene diepoxy modified (meth)acrylate include 1,2-ethylenediol diepoxy (meth)acrylate, 1,3-propanediol diepoxy (meth)acrylate, 1,4-butanediol diepoxy (meth)acrylate, 1,5-pentanediol diepoxy (meth)acrylate, 1,6-hexanediol diepoxy (meth)acrylate, 1,7-heptanediol diepoxy (meth)acrylate, 1,8-octanediol diepoxy (meth)acrylate, 1,9-nonanediol diepoxy (meth)acrylate, 1,10-decanediol diepoxy (meth)acrylate, and neopentyl glycol diepoxy (meth)acrylate.

[0077] Examples of the polyalkylene di(meth)acrylate include diethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, and tripropylene glycol di(meth)acrylate.

[0078] Examples of polyalkylene dialkylene oxide-modified (meth)acrylates include diethylene glycol di(ethylene oxide-modified (meth)acrylate), dipropylene glycol di(ethylene oxide-modified (meth)acrylate), triethylene glycol (ethylene oxide-modified (meth)acrylate), and tripropylene glycol (ethylene oxide-modified (meth)acrylate).

[0079] Examples of the polyalkylene diepoxy modified (meth)acrylate include diethylene glycol diepoxy (meth)acrylate, dipropylene glycol diepoxy (meth)acrylate, triethylene glycol diepoxy (meth)acrylate, and tripropylene glycol diepoxy (meth)acrylate.

[0080] <Bisphenol A di(alkylene oxide modified or epoxy modified)(meth)acrylate> Bisphenol A di(alkylene oxide-modified or epoxy-modified)(meth)acrylate is a compound represented by formula (F') or the like. [ka] [In the formula, R b21’ ~R b22 ’ are each independently [ka] In the formula, q is an integer of 0 to 16, and R 1’ ~R 3 ’ are each independently a hydrogen atom or an alkyl group, R 1’ may be different groups for each unit. It is.]

[0081] Examples of bisphenol A dialkylene oxide modified (meth)acrylates include bisphenol A di(ethylene oxide modified (meth)acrylate) and bisphenol A di(propylene oxide modified (meth)acrylate).

[0082] (Urethane poly(meth)acrylate) Examples of the urethane poly(meth)acrylate include a reaction product of a compound group containing a hydroxyl group-containing poly(meth)acrylate and a polyisocyanate.

[0083] <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.

[0084] The polyisocyanates may be used alone or in combination of two or more.

[0085] <Polyisocyanate> "Polyisocyanate" means a compound that has two or more isocyanate groups (-N=C=O).

[0086] Examples of the polyisocyanate include linear aliphatic polyisocyanates, branched aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic polyisocyanates, and biuret forms, isocyanurate forms, allophanate forms, adduct forms, and the like thereof.

[0087] 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.

[0088] Examples of the branched aliphatic polyisocyanate include diethylpentylene diisocyanate, trimethylbutylene diisocyanate, trimethylpentylene diisocyanate, and trimethylhexamethylene diisocyanate.

[0089] Examples of the alicyclic polyisocyanate include monocyclic alicyclic polyisocyanates, crosslinked cyclic alicyclic polyisocyanates, and condensed cyclic alicyclic polyisocyanates.

[0090] Examples of the monocyclic alicyclic polyisocyanate include hydrogenated xylene diisocyanate, isophorone diisocyanate, cyclopentylene diisocyanate, cyclohexylene diisocyanate, cycloheptylene diisocyanate, cyclodecylene diisocyanate, 3,5,5-trimethylcyclohexylene diisocyanate, and dicyclohexylmethane diisocyanate.

[0091] Examples of the crosslinked alicyclic polyisocyanate include tricyclodecylene diisocyanate, adamantane diisocyanate, and norbornene diisocyanate.

[0092] An example of the condensed ring alicyclic polyisocyanate is bicyclodecylene diisocyanate.

[0093] Examples of the aromatic polyisocyanate include monocyclic aromatic polyisocyanates and condensed ring aromatic polyisocyanates.

[0094] Examples of the monocyclic aromatic polyisocyanate include dialkyl diphenylmethane diisocyanates such as 4,4'-diphenyldimethylmethane diisocyanate, tetraalkyl diphenylmethane 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.

[0095] The condensed ring aromatic polyisocyanate may, for example, be 1,5-naphthylene diisocyanate.

[0096] (Carboxyl group-containing poly(meth)acrylate) In one embodiment, the poly(meth)acrylate is preferably a carboxyl group-containing poly(meth)acrylate.

[0097] Examples of the carboxyl group-containing poly(meth)acrylate include a reaction product of a hydroxyl group-containing poly(meth)acrylate with a carboxylic acid anhydride.

[0098] Examples of carboxylic acid anhydrides include phthalic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, nadic anhydride, methylnadic anhydride, maleic anhydride, itaconic anhydride, and succinic anhydride.

[0099] Examples of the product (carboxyl group-containing poly(meth)acrylate) include ARONIX M510 (acid value: 80 mgKOH / g to 120 mgKOH / g, manufactured by Toagosei Co., Ltd.) and ARONIX M520 (acid value: 20 mgKOH / g to 40 mgKOH / g, manufactured by Toagosei Co., Ltd.).

[0100] In one embodiment, the carboxyl group-containing poly(meth)acrylate is preferably a reaction product of pentaerythritol tri(meth)acrylate or dipentaerythritol penta(meth)acrylate with a carboxylic acid anhydride, more preferably a reaction product of pentaerythritol tri(meth)acrylate with a carboxylic acid anhydride, and even more preferably a reaction product of pentaerythritol tri(meth)acrylate with a succinic acid anhydride. The reason why it is preferable is, for example, improvement of scratch resistance.

[0101] In one embodiment, the mass% content (poly(meth)acrylate / active energy ray curable composition nonvolatile content) is, for example, 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%, 1 mass%, 0.1 mass%, 0.01 mass%, etc. In one embodiment, the content is preferably 0.01 mass% to 90 mass%, more preferably 10 mass% to 90 mass%, and even more preferably 25 mass% to 75 mass%.

[0102] <Particle> The particles may be used alone or in combination of two or more types.

[0103] Examples of the particles include inorganic particles and organic particles.

[0104] (Inorganic particles) Examples of the inorganic particles include hollow inorganic particles and solid inorganic particles.

[0105] <Hollow inorganic particles> Examples of hollow inorganic particles include hollow silica particles, hollow aluminosilicate particles, hollow alumina particles, hollow mullite particles, hollow titanium oxide particles, hollow magnesium fluoride particles, and fly ash balloons.

[0106] In one embodiment, the hollow inorganic particles are preferably surface-modified hollow inorganic particles. Examples of the modified hollow inorganic particles include (meth)acrylic-modified hollow inorganic particles and silicone-modified hollow inorganic particles.

[0107] Examples of the mass % content (modified portion / modified hollow inorganic particles) include 40 mass %, 35 mass %, 30 mass %, 25 mass %, 20 mass %, 15 mass %, 10 mass %, 5 mass %, 1 mass %, 0.1 mass %, 0.01 mass %, etc. In one embodiment, the content is preferably 0.01 mass % to 40 mass %, more preferably 0.1 mass % to 30 mass %, and even more preferably 1 mass % to 20 mass %.

[0108] Examples of the product (hollow inorganic particles) include Sururia 5320, 4320, 4110, 2320, 1110, JX1008SIV, JX1009SIV (manufactured by JGC Catalysts and Chemicals Industries, Ltd.), and Silinax (manufactured by Nittetsu Mining Co., Ltd.).

[0109] <Solid inorganic particles> Examples of the solid inorganic particles include solid aluminum oxide particles (solid alumina particles), solid titanium oxide particles, solid zirconium oxide particles, solid niobium oxide particles, solid barium titanate particles, and solid zinc oxide particles.

[0110] Examples of products (solid inorganic particles) include Alumisol F-3000 (Kawaken Fine Chemical Co., Ltd.), Bylar AL-7 (Taki Chemical Co., Ltd.), NANOBYK-3611 (BYK Chemie), and Optisol LAA530U (RANCO).

[0111] (organic particles) Examples of the organic particles include acrylic particles, styrene-acrylic particles, polystyrene particles, polyacrylonitrile particles, melamine particles, polyethylene particles, and benzoguanamine particles.

[0112] Examples of the organic particles include solid organic particles, hollow organic particles, etc. In one embodiment, the organic particles are preferably hollow organic particles.

[0113] In one embodiment, the organic particles are preferably acrylic particles or styrene-acrylic particles, more preferably crosslinked acrylic particles or crosslinked styrene-acrylic particles, and even more preferably crosslinked methyl methacrylate particles or crosslinked methyl methacrylate-styrene particles.

[0114] "A particles" refers to particles containing A resin as a raw material.

[0115] Examples of commercially available products (acrylic particles) include Eposter MA1004, MA1006 (manufactured by Nippon Shokubai Co., Ltd.), Tuftic FH-S005 (manufactured by Nippon Exlan Kogyo Co., Ltd.), Chemisnow MX-80H3wT, MX-150, MX-180TA, MX-300, MX-500, MX-1000, MX-1500H, MX-2000, MX-3000 (manufactured by Soken Chemical Industries Co., Ltd.), Techpolymer MBX-5, MBX-8, SSX-101, SSX-102, SSX-103, SSX-105, SSX-108, SSX-110, SSX-115HXE, SSX-120, and SSX-127 (manufactured by Sekisui Chemical Co., Ltd.).

[0116] Examples of commercially available products (styrene-acrylic particles) include Eposter MA2003 (manufactured by Nippon Shokubai Co., Ltd.), Techpolymer MSX, SMX (manufactured by Sekisui Plastics Co., Ltd.), and the like.

[0117] Examples of commercially available products (polystyrene particles) include Techpolymer NX series, Techpolymer SBX-4 (manufactured by Sekisui Chemical Co., Ltd.), Chemisnow SX-130H, SX-350H, and SX-500H (manufactured by Soken Chemical Industries, Ltd.).

[0118] An example of a commercially available product (polyacrylonitrile particles) is Tuftic ASF (manufactured by Nippon Exlan Kogyo Co., Ltd.).

[0119] Examples of commercially available products (melamine particles) include Eposter SS, Eposter S, Eposter FS, Eposter S6, and Eposter S12 (manufactured by Nippon Shokubai Co., Ltd.).

[0120] Examples of commercially available products (polyethylene particles) include Mipelon XM-220 and XM221U (manufactured by Mitsui Chemicals, Inc.), Flow Beads LE-1080 (manufactured by Sumitomo Seika Chemicals, Inc.), and Chemipearl W500 (manufactured by Mitsui Chemicals, Inc.).

[0121] Examples of commercially available products (benzoguanamine particles) include Eposter MS, M05, and L15 (manufactured by Nippon Shokubai Co., Ltd.).

[0122] Examples of the production method (organic particles) include a nozzle vibration method, an SPG membrane emulsification method, a microchannel method, a soap-free emulsion polymerization method, a dispersion polymerization method, a suspension polymerization method, and a seed emulsion polymerization method.

[0123] (Physical properties, etc. (particles)) Examples of particle diameters (inorganic particles) include 100 nm, 95 nm, 90 nm, 85 nm, 80 nm, 75 nm, 70 nm, 65 nm, 60 nm, 55 nm, 50 nm, 45 nm, 40 nm, 35 nm, 30 nm, 25 nm, 20 nm, 15 nm, 10 nm, and 5 nm. In one embodiment, the particle diameter is preferably 5 nm to 100 nm. The reason why this is preferable is, for example, hardness, flexibility, and the like.

[0124] Examples of particle diameters (organic particles) include 100 nm, 95 nm, 90 nm, 85 nm, 80 nm, 75 nm, 70 nm, 65 nm, 60 nm, 55 nm, 50 nm, 45 nm, 40 nm, 35 nm, 30 nm, 25 nm, 20 nm, 15 nm, 10 nm, and 5 nm. In one embodiment, the particle diameter is preferably 5 nm to 100 nm. The reason why this is preferable is, for example, hardness and flexibility.

[0125] The particle size is a volume average particle size. The volume average particle size is the particle size at which the volume-based particle size distribution is 50% when integrated from the small particle size side in the volume-based particle size distribution measured by dynamic light scattering.

[0126] The volumetric particle size distribution can be measured by the following procedure. <Inorganic particles> (1) Preparation of measurement solution A solution is prepared by adding a measurement sample (particles) to propylene glycol monomethyl ether (PGME, for example, manufactured by Nippon Nyukazai) so that the measurement sample concentration becomes 1% by mass. (2) Measurement of particle size distribution by volume Measuring equipment: Dynamic light scattering particle size distribution measuring device "LB-550" (HORIBA, Ltd.) Number of measurements: 5 Measurement temperature: 25±0.5℃ Measurement time: 60 seconds Measurement upper limit: 6000nm Measurement lower limit: 1nm Measurement solvent: Refractive index of PGME: 1.404

[0127] Examples of the particle shape include spherical, hollow, solid, porous, rod-like, plate-like, fibrous, and amorphous.

[0128] Examples of the particles include hydrophilic particles and hydrophobic particles.

[0129] Examples of the mass% content (particles / non-volatile content of active energy ray-curable composition) include 82 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%, 3 mass%, etc. In one embodiment, the content is preferably 3 mass% to 82 mass%.

[0130] Examples of the mass% content (inorganic particles / nonvolatile content of active energy ray-curable composition) include 82 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%, 3 mass%, 1 mass%, 0 mass%, etc. In one embodiment, the content is preferably 0 mass% to 82 mass%.

[0131] Examples of the mass% content (hollow inorganic particles / nonvolatile content of active energy ray-curable composition) include 82 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%, 3 mass%, 1 mass%, 0 mass%, etc. In one embodiment, the content is preferably 0 mass% to 82 mass%.

[0132] Examples of the mass% content (solid inorganic particles / nonvolatile content of active energy ray-curable composition) include 15 mass%, 14 mass%, 13 mass%, 12 mass%, 11 mass%, 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 15 mass%, more preferably 2 mass% to 15 mass%, and even more preferably 6 mass% to 15 mass%.

[0133] Examples of the mass% content (organic particles / nonvolatile content of active energy ray-curable composition) include 82 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%, 3 mass%, 1 mass%, 0 mass%, etc. In one embodiment, the content is preferably 0 mass% to 82 mass%.

[0134] <Phosphate ester> The phosphate esters may be used alone or in combination of two or more.

[0135] Examples of the phosphate ester include polyoxyalkylene alkyl ether phosphate ester, polyoxyalkylene aryl ether phosphate ester, poly(oxyalkylene) poly(aryloxide) ether phosphate ester, and the like.

[0136] Examples of polyoxyalkylene alkyl ether phosphate esters include polyoxyethylene lauryl ether phosphate ester, polyoxyethylene alkyl (C8) ether phosphate ester, polyoxyethylene alkyl (C12,13) ​​ether phosphate ester, polyoxyethylene alkyl (C10) ether phosphate ester, polyoxyethylene tridecyl ether phosphate ester, polyoxyethylene tridecyl ether phosphate ester, polyoxyethylene lauryl ether phosphate ester, polyoxyethylene lauryl ether phosphate monoethanolamine salt, and polyoxyethylene alkyl (C8) ether phosphate monoethanolamine salt.

[0137] Examples of the polyoxyalkylene aryl ether phosphate ester include polyoxyethylene styrenated phenyl ether phosphate ester and polyoxyethylene styrenated phenyl ether phosphate ester.

[0138] Examples of poly(oxyalkylene) poly(aryloxide) ether phosphate esters include poly(oxyethylene) poly(styrene oxide) ether phosphate esters.

[0139] Examples of the product (phosphate ester) include Plysurf A208B, A208F, A208N, A210D, A212C, A215C, A219B, AL, AL 12H, DB-01, DB-02, DBS, DOM, and M208F (all manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), TEGO DISPERS 655 (manufactured by EVONIK), and Light Ester P-1M (manufactured by Kyoeisha Chemical Co., Ltd.).

[0140] In one embodiment, the phosphate ester is preferably a polyoxyalkylene structure-containing phosphate ester, more preferably a polyoxyethylene structure-containing phosphate ester, even more preferably a polyoxyethylene structure- and phenyl group-containing phosphate ester, and particularly preferably a polyoxyethylene structure- and styrene-like structure-containing phosphate ester.

[0141] Examples of the styrene-like structure include a styrene oxide unit and a styrenated phenyl group.

[0142] In one embodiment, the phosphate ester is preferably a phosphate ester that does not contain a polymerizable unsaturated bond.

[0143] Examples of the acid value (phosphate ester) include 550 mgKOH / g, 540 mgKOH / g, 500 mgKOH / g, 450 mgKOH / g, 425 mgKOH / g, 400 mgKOH / g, 350 mgKOH / g, 300 mgKOH / g, 250 mgKOH / g, 200 mgKOH / g, 195 mgKOH / g, 175 mgKOH / g, 160 mgKOH / g, 150 mgKOH / g, 125 mgKOH / g, 100 mgKOH / g, 95 mgKOH / g, 70 mgKOH / g, 50 mgKOH / g, 30 mgKOH / g, 20 mgKOH / g, 10 mgKOH / g, 5 mgKOH / g, and 0 mgKOH / g. In one embodiment, the acid value is preferably 0 mgKOH / g to 550 mgKOH / g, and more preferably 0 mgKOH / g to 400 mgKOH / g.

[0144] Examples of the mass % content (phosphate ester / active energy ray-curable composition nonvolatile content) are 10 mass %, 9 mass %, 8 mass %, 7 mass %, 6 mass %, 5 mass %, 4 mass %, 3 mass %, 2 mass %, 1 mass %, 0.5 mass %, 0.1 mass %, etc. In one embodiment, the content is preferably 0.1 mass % to 10 mass %, more preferably 0.1 mass % to 6 mass %, and even more preferably 0.5 mass % to 2 mass %.

[0145] <(Meth)acryloyl group-containing perfluoropolyether> In one embodiment, the coating agent may contain a (meth)acryloyl group-containing perfluoropolyether. The (meth)acryloyl group-containing perfluoropolyether may be used alone or in combination of two or more kinds.

[0146] "(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 a perfluoroalkylene ether is a repeating unit.

[0147] Examples of the (meth)acryloyl group-containing perfluoropolyether include perfluoropolyether containing (meth)acryloyl groups at both ends and perfluoropolyether containing a (meth)acryloyl group at one end.

[0148] Examples of the product ((meth)acryloyl group-containing perfluoropolyether) include KY-1203, KY-1207 (manufactured by Shin-Etsu Chemical Co., Ltd.), and Optool DAC-HP (manufactured by Daikin Corporation).

[0149] In one embodiment, the (meth)acryloyl group-containing perfluoropolyether is preferably silicon atom and (meth)acryloyl group-containing perfluoropolyether. The product (silicon atom and (meth)acryloyl group-containing perfluoropolyether) is, for example, KY-1203.

[0150] Examples of the mass % content ((meth)acryloyl group-containing perfluoropolyether / nonvolatile content of active energy ray-curable composition) 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 5 mass %.

[0151] <Photopolymerization initiator> In one embodiment, the active energy ray-curable composition may optionally contain a photopolymerization initiator. The photopolymerization initiator may be used alone or in combination of two or more kinds.

[0152] 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.

[0153] Examples of the photopolymerization initiator containing an α-hydroxydimethylacetophenone group 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.

[0154] Examples of α-hydroxycycloalkylphenones include 1-hydroxycyclohexyl phenyl ketone.

[0155] Examples of α-aminoalkylphenones include 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one.

[0156] An example of the benzyl dimethyl ketal is 2,2-dimethoxy-1,2-diphenylethan-1-one.

[0157] 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.

[0158] Examples of unsubstituted or substituted benzyl include benzyl and p-anisyl.

[0159] 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.

[0160] Examples of the acylphosphine oxide include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, and the like.

[0161] Examples of the substituted thioxanthone include 2-chlorothioxanthone, 2-isopropylthioxanthone, and 2,4-diethylthioxanthone.

[0162] 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).

[0163] When electron beam curing is used, a photoinitiator is not necessary.

[0164] Examples of the mass % content (photopolymerization initiator / non-volatile content of active energy ray-curable composition) 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 %.

[0165] <Organic solvent> 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.

[0166] Examples of the organic solvent include ketone solvents, aromatic solvents, alcohol solvents, glycol solvents, glycol ether solvents, ester solvents, petroleum solvents, haloalkane solvents, and amide solvents.

[0167] Examples of the ketone solvent include methyl ethyl ketone, acetylacetone, methyl isobutyl ketone, cyclopentanone, and cyclohexanone.

[0168] Examples of aromatic solvents include toluene and xylene.

[0169] Examples of the alcohol solvent include methanol, ethanol, n-propanol, isopropanol, n-butanol, i-butanol, and t-butanol.

[0170] Examples of the glycol solvent include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, polyethylene glycol, and polypropylene glycol.

[0171] 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.

[0172] Examples of the ester solvent include ethyl acetate, butyl acetate, methyl cellosolve acetate, ethyl cellosolve acetate, and propylene glycol monomethyl ether acetate.

[0173] Examples of the petroleum solvent include Solvesso #100 (manufactured by Exxon Corporation) and Solvesso #150 (manufactured by Exxon Corporation).

[0174] The haloalkane solvent may, for example, be chloroform.

[0175] The amide solvent may, for example, be dimethylformamide.

[0176] 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%, 0 mass%, etc. In one embodiment, the content is preferably 0 mass% to 99 mass%.

[0177] <Additives> The active energy ray-curable composition may optionally contain an agent (additive) that does not fall into any of the above categories.

[0178] Examples of the additives include ultraviolet absorbers, antifoaming agents, surface conditioners, antifouling agents, and pigments.

[0179] In one embodiment, the content by weight (additive / non-volatile content of active energy ray-curable composition) is preferably less than 5 parts by weight, less than 1 part by weight, less than 0.1 parts by weight, less than 0.01 parts by weight, 0 parts by weight, etc.

[0180] In one embodiment, the part by mass content (additive / poly(meth)acrylate), part by mass content (additive / particles), part by mass content (additive / phosphate ester), part by mass content (additive / photopolymerization initiator), and part by mass content (additive / organic solvent) are preferably less than 5 parts by mass, less than 1 part by mass, less than 0.1 parts by mass, less than 0.01 parts by mass, 0 parts by mass, and the like.

[0181] By dispersing and mixing the above-mentioned agents, an active energy ray-curable composition can be produced.

[0182] Examples of the dispersing and mixing means include an emulsifying disperser and an ultrasonic dispersing device.

[0183] Examples of uses (of the active energy ray-curable composition) include coating agents, hard coating agents, low refractive index coating agents, low refractive index hard coating agents, coating agents for optical films, hard coating agents for optical films, and low refractive index hard coating agents for optical films.

[0184] [Cured product] The present disclosure relates to a cured product of the above-mentioned active energy ray-curable composition.

[0185] The curing conditions are, for example, as follows:

[0186] [Laminate] The present disclosure relates to a laminate comprising the above-mentioned cured product.

[0187] The production method (laminate) may be, 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 forming a cured layer of an active energy ray curable composition by irradiating with active energy rays

[0188] Examples of the substrate include polycarbonate films, acrylic films (polymethyl methacrylate films, etc.), polystyrene films, polyester films, polyolefin films, epoxy resin films, melamine resin films, triacetyl cellulose films, ABS films, AS films, norbornene-based resin films, cyclic olefin films, and polyvinyl alcohol films.

[0189] In one embodiment, the thickness (base material) is preferably 10 μm to 2000 μm.

[0190] In one embodiment, the thickness (of the cured layer) is preferably 0.05 μm to 20 μm.

[0191] (Coating process) Examples of the coating method include bar coater coating, wire bar coating, Mayer bar coating, air knife coating, gravure coating, reverse gravure coating, flow coat coating, offset printing, flexographic printing, and screen printing.

[0192] (Active energy ray curing process) Examples of the active energy rays include ultraviolet rays and electron beams.

[0193] Examples of ultraviolet light sources include a xenon lamp, a high-pressure mercury lamp, and a metal halide lamp.

[0194] When a high pressure mercury lamp is used, the curing conditions are preferably the following conditions. Lamp power: 25W / cm~160W / cm UV illuminance: 10mW / cm 2 ~800mW / cm 2 Accumulated light output: 25mJ / cm 2 ~2000mJ / cm 2 Conveying speed: 1m / min to 50m / min

[0195] When an electron beam is used, the curing conditions are preferably as follows: Acceleration voltage: 10kV~300kV Conveying speed: 5m / min to 50m / min EXAMPLES

[0196] The present invention will be specifically described 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.

[0197] Example 1: Active energy ray curable composition The substances shown in the table below were mixed as non-volatile components, and then the mixture was diluted with methyl isobutyl ketone to obtain an active energy ray-curable composition (non-volatile content: 10%).

[0198] Unless otherwise stated, other examples were carried out in the same manner as above, except for the changes shown in the table below.

[0199] [Table 1] [Table 2]

[0200] Viscoat #300: Pentaerythritol polyacrylate, manufactured by Osaka Organic Chemical Industry Co., Ltd. NK Ester A-9550: Dipentaerythritol polyacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd. Surulia 2320: Hollow silica particles, particle size 50 nm, refractive index 1.30, manufactured by JGC Catalysts and Chemicals Co., Ltd. Surulia 4320: Hollow silica particles, particle size 60 nm, refractive index 1.25, manufactured by JGC Catalysts and Chemicals Co., Ltd. Surulia 5320: Hollow silica particles, particle size 75 nm, refractive index 1.21, manufactured by JGC Catalysts and Chemicals Co., Ltd. NANOBYK-3611: solid alumina particles, manufactured by BYK Chemie DISPERS 655: Polyethylene oxide and styrene oxide unit-containing phosphate ester, product name "TEGO DISPERS 655", manufactured by EVONIK Plysurf A212C: Polyoxyethylene tridecyl ether phosphate ester, manufactured by Daiichi Kogyo Seiyaku Co., Ltd. Light Ester P-1M: 2-Methacryloyloxyethyl phosphate ester, manufactured by Kyoeisha Chemical Co., Ltd. KY-1203: Perfluoropolyether containing silicon atoms and (meth)acryloyl groups, product name "KY-1203", manufactured by Shin-Etsu Chemical Co., Ltd. DAC-HP: (Meth)acryloyl group-containing perfluoropolyether, product name "OPTOOL DAC-HP", manufactured by Daikin Corporation

[0201] (Production Example 1: Production of anchoring agent) An anchoring agent with a solid content of 40% by mass was prepared by mixing 66 parts by mass of aliphatic urethane acrylate (product name "BEAMSET 577", manufactured by Arakawa Chemical Industries Co., Ltd.), 22 parts by mass of dipentaerythritol polyacrylate (product name "NK Ester A-9550", manufactured by Shin-Nakamura Chemical Co., Ltd.), 9 parts by mass of (product name "NANOBYK-3611", 30% by mass methoxypropyl acetate, manufactured by BYK Chemie), and 3 parts by mass of 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-methylpropanone (product name "Omnirad 2959", manufactured by IGM Resins) and diluting with methyl isobutyl ketone. (Laminate) The anchor agent was applied to a polyethylene terephthalate film (product name "Lumirror 50U48", Toray Industries, Inc., film thickness: 50 μm) so that the film thickness after drying would be 3 to 5 μm, and after drying at 80 °C for 1 minute, it was irradiated with active energy rays in an air atmosphere (ultraviolet ray irradiation: 250 mW / cm 2 , 200mJ / cm 2 The active energy ray-curable coating agent (1) was applied to the hard coat surface so that the film thickness after drying would be 0.1 μm, and after drying at 80° C. for 1 minute, it was irradiated with active energy rays in a nitrogen atmosphere (ultraviolet ray irradiation: 250 mW / cm 2 , 600mJ / cm 2 ) and cured to obtain a laminate.

[0202] <Scratch resistance> The cured product was inspected for scratch resistance using a steel wool tool. Test load, area, number of strokes: As shown in the table Steel wool: #0000 ○: 5 or less scratches △: 6 to less than 10 scratches ×: 10 or more scratches

Claims

1. An active energy ray-curable composition, The active energy ray-curable composition includes poly(meth)acrylate, particles, and a phosphoric acid ester.

2. 2. The active energy ray-curable composition according to claim 1, comprising 0.1% by mass to 10% by mass of a phosphoric acid ester relative to 100% by mass of the nonvolatile content of the active energy ray-curable composition.

3. A cured product of the active energy ray-curable composition according to claim 1 or 2.

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

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