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: The active energy ray-curable composition contains a polymer, a poly(meth)acrylate containing no urethane bond, and a urethane poly(meth)acrylate. The polymer has a glass transition temperature of 50°C or higher.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 hardness and flexibility and has good coatability. [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 comprises a polymer, a urethane bond-free poly(meth)acrylate, and a urethane poly(meth)acrylate, The glass transition temperature of the polymer is 50° C. or higher. An active energy ray-curable composition. (Item 2) The active energy ray-curable composition according to the preceding item, comprising particles. (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 active energy ray-curable composition of the present invention exhibits good coatability, and the cured product of the present invention exhibits good hardness and flexibility. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0008] Throughout the present disclosure, the range of the values ​​of each physical property, content, 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 ... 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 amount (A / B)" means the β amount (α) of A relative to 100α of B. α can be, for example, mass %, mol %, parts by mass, etc. β amount can be, for example, content, amount used, etc. "Content (% by mass) (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 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 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] A "branched alkyl group" means a group in which at least one hydrogen atom of a linear alkyl group is replaced with an alkyl group, and which does not have a cyclic structure.

[0017] Examples of the branched alkyl group include an i-propyl group, a diethylpentyl group, a trimethylbutyl group, a trimethylpentyl group, and a trimethylhexyl group.

[0018] 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.

[0019] "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.

[0020] 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.

[0021] Examples of the bridged ring cycloalkyl group include a tricyclodecyl group, an adamantyl group, and a norbornyl group.

[0022] 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.

[0023] 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.

[0024] Examples of the alkylene group include a straight-chain alkylene group, a branched alkylene group, and a cycloalkylene group.

[0025] Examples of the straight-chain alkylene group include a methylene group, an ethylene group, an n-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.

[0026] Examples of the branched alkylene group include a diethylpentylene group, a trimethylbutylene group, a trimethylpentylene group, and a trimethylhexylene group.

[0027] 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.

[0028] 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.

[0029] Examples of the bridged ring cycloalkylene group include a tricyclodecylene group, an adamantylene group, and a norbornylene group.

[0030] Examples of the fused ring cycloalkylene group include a bicyclodecylene group.

[0031] The alkylene group also includes a group formed by combining a linear alkylene group, a branched alkylene group, and a cycloalkylene group. Examples of the combined group include a cycloalkylene alkylene group and an alkylene cycloalkylene alkylene group.

[0032] 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.

[0033] 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.

[0034] 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.

[0035] Examples of the aryl group include a monocyclic aryl group and a condensed ring aryl group.

[0036] Examples of the monocyclic aryl group include a phenyl group, a tolyl group, and a mesityl group.

[0037] The fused ring aryl group may, for example, be a naphthyl group.

[0038] Examples of the arylene group include a monocyclic arylene group and a fused ring arylene group.

[0039] Examples of the monocyclic arylene group include a phenylene group and a tolylene group.

[0040] The fused ring arylene group may, for example, be a naphthylene group.

[0041] [Active energy ray-curable composition] The present disclosure relates to an active energy ray-curable composition, the active energy ray-curable composition comprising a polymer, a urethane bond-free poly(meth)acrylate, and a urethane poly(meth)acrylate, the polymer having a glass transition temperature of 50° C. or higher.

[0042] <Polymer> The polymers may be used alone or in combination of two or more.

[0043] (non-polar monomer unit) The polymer may include non-polar monomer units. The non-polar monomers may be used alone or in combination of two or more.

[0044] Examples of the non-polar monomer include unsubstituted (meth)acrylic acid alkyl esters and alkenylaryl compounds.

[0045] Examples of the unsubstituted (meth)acrylic acid alkyl ester include unsubstituted straight-chain (meth)acrylic acid alkyl esters, unsubstituted branched (meth)acrylic acid alkyl esters, and unsubstituted alicyclic (meth)acrylic acid alkyl esters.

[0046] Examples of unsubstituted linear alkyl (meth)esters of (meth)acrylic acid include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, n-amyl (meth)acrylate, n-hexyl (meth)acrylate, n-octyl (meth)acrylate, n-nonyl (meth)acrylate, n-decyl (meth)acrylate, n-undecyl (meth)acrylate, lauryl (meth)acrylate, tridecyl (meth)acrylate, myristyl (meth)acrylate, pentadecyl (meth)acrylate, palmityl (meth)acrylate, heptadecyl (meth)acrylate, and stearyl (meth)acrylate.

[0047] Examples of unsubstituted branched alkyl (meth)acrylates include i-propyl (meth)acrylate, i-butyl (meth)acrylate, i-amyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate.

[0048] Examples of the unsubstituted alicyclic alkyl (meth)acrylate ester include cyclohexyl (meth)acrylate.

[0049] Examples of the alkenylaryl compound include styrene, α-methylstyrene, p-methylstyrene, vinyltoluene, and divinylbenzene.

[0050] Examples of the mass% content (non-polar monomer unit / polymer) include 99 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%, 2 mass%, 1 mass%, 0 mass%, etc. In one embodiment, the content is preferably 0 mass% to 99 mass%, more preferably 60 mass% to 99 mass%, and even more preferably 65 mass% to 95 mass%.

[0051] Examples of the molar content (non-polar monomer unit / polymer) include 99 mol%, 96 mol%, 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 99 mol%, more preferably 50 mol% to 99 mol%, and even more preferably 65 mol% to 96 mol%. The reason for this preference is, for example, improvement of leveling property, improvement of compatibility, and the like.

[0052] (Hydroxyl Group-Containing Monomer Unit) The polymer may contain hydroxyl-containing monomer units. The hydroxyl-containing monomers may be used alone or in combination of two or more.

[0053] Examples of the hydroxyl group-containing monomer include hydroxyl group-containing (meth)acrylic esters and hydroxyl group-containing vinyl ethers.

[0054] Examples of the hydroxyl group-containing (meth)acrylic acid ester include a hydroxyl group-containing linear (meth)acrylic acid ester and a hydroxyl group-containing branched (meth)acrylic acid ester.

[0055] Examples of hydroxyl group-containing linear (meth)acrylic acid esters include 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate.

[0056] Examples of hydroxyl group-containing branched (meth)acrylic acid esters include 1-hydroxyethyl (meth)acrylate, 1-hydroxypropyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxy-1-methylethyl (meth)acrylate, 1-hydroxy-2-methylpropyl (meth)acrylate, 1-hydroxybutyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 1-hydroxy-1-methylpropyl (meth)acrylate, 2-hydroxy-1-methylpropyl (meth)acrylate, 3-hydroxy-1-methylpropyl (meth)acrylate, 1-ethyl-2-hydroxyethyl (meth)acrylate, 1-hydroxy-2-methylpropyl (meth)acrylate, 2-hydroxy-2-methylpropyl (meth)acrylate, 3-hydroxy-2-methylpropyl (meth)acrylate, and 1,1-dimethyl-2-hydroxyethyl (meth)acrylate.

[0057] Examples of the hydroxyl group-containing vinyl ether include hydroxyalkyl vinyl ether and polyalkylene glycol monovinyl ether.

[0058] Examples of the hydroxyalkyl vinyl ether include a hydroxy linear alkyl vinyl ether, a hydroxy branched alkyl vinyl ether, and a hydroxycycloalkyl vinyl ether.

[0059] Examples of the polyalkylene glycol monovinyl ether include polymethylene glycol monovinyl ether, polyethylene glycol monovinyl ether, and polypropylene glycol monovinyl ether.

[0060] Examples of the mass% content (hydroxyl group-containing monomer unit / polymer) include 40 mass%, 35 mass%, 30 mass%, 25 mass%, 20 mass%, 15 mass%, 10 mass%, 5 mass%, 2 mass%, 1 mass%, 0 mass%, etc. In one embodiment, the content is preferably 0 mass% to 40 mass%, more preferably 1 mass% to 40 mass%, and even more preferably 5 mass% to 30 mass%.

[0061] Examples of the molar content (hydroxyl group-containing monomer unit / polymer) include 40 mol%, 35 mol%, 30 mol%, 25 mol%, 20 mol%, 15 mol%, 10 mol%, 5 mol%, 4 mol%, 2 mol%, 1 mol%, 0 mol%, etc. In one embodiment, the content is preferably 0 mol% to 40 mol%, more preferably 4 mol% to 35 mol%. Reasons for this being preferable include, for example, improved leveling properties and improved compatibility.

[0062] (Other building blocks) The polymer may optionally contain structural units (other structural units) other than the non-polar monomer units and the hydroxyl group-containing monomer units.

[0063] Examples of monomers other than those mentioned above include (meth)acrylic acid, (meth)acrylamide, (meth)acrylonitrile, and polyfunctional (meth)acrylates.

[0064] Examples of the polyfunctional (meth)acrylate include ethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, and pentaerythritol tetra(meth)acrylate.

[0065] Examples of the mass % content (other structural units / polymer) include less than 10 mass %, less than 5 mass %, less than 2 mass %, less than 1 mass %, less than 0.1 mass %, and 0 mass %.

[0066] The mass% content (any one of other structural units / non-polar monomer units, hydroxyl group-containing monomer units, and hydroxyl group-containing structural units) can be, for example, less than 10 mass%, less than 5 mass%, less than 2 mass%, less than 1 mass%, less than 0.1 mass%, or 0 mass%, etc.

[0067] Examples of the mol % content (other structural units / polymer) include less than 10 mol %, less than 5 mol %, less than 2 mol %, less than 1 mol %, less than 0.1 mol %, and 0 mol %.

[0068] The molar percentage content (one of other structural units / non-polar monomer units, hydroxyl group-containing monomer units, and hydroxyl group-containing structural units) can be, for example, less than 10 mol%, less than 5 mol%, less than 2 mol%, less than 1 mol%, less than 0.1 mol%, or 0 mol%, etc.

[0069] <Physical properties (polymer)> Examples of the glass transition temperature (polymer) include 190°C, 185°C, 180°C, 170°C, 160°C, 150°C, 140°C, 130°C, 120°C, 115°C, 110°C, 105°C, 103°C, 101°C, 100°C, 90°C, 85°C, 80°C, 75°C, 70°C, 65°C, 60°C, 55°C, and 50°C. In one embodiment, the glass transition temperature of the component (A) is preferably 50°C to 190°C, and more preferably 90°C to 190°C.

[0070] The glass transition temperature is measured under the following conditions. Differential scanning calorimeter: Product name "DSC8230B", manufactured by Rigaku Corporation Heating rate: 10℃ / min

[0071] When the amount of monomer used in polymer production can be accurately determined and the polymerization rate is high, the glass transition temperature can be calculated using the Fox equation. Fox formula: 1 / Tg = (Wa / Tga) + (Wb / Tgb) + ··· + (Wn / Tgn) Tg: Glass transition temperature of the copolymer (K) Wa: mass% of monomer A Tga: Glass transition temperature of homopolymer of monomer A (K) Wb: mass% of monomer B Tgb: Glass transition temperature of homopolymer of monomer B (K) Wn: mass% of monomer N Tgn: Glass transition temperature of homopolymer of monomer N (K)

[0072] The hydroxyl value (polymer) is, for example, 175 mgKOH / g, 172 mgKOH / g, 170 mgKOH / g, 165 mgKOH / g, 160 mgKOH / g, 155 mgKOH / g, 150 mgKOH / g, 145 mgKOH / g, 140 mgKOH / g, 135 mgKOH / g, 130 mgKOH / g, 125 mgKOH / g, 120 mgKOH / g, 115 mgKOH / g, 110 mgKOH / g, 105 mgKOH / g, 100 mgKOH / g, 95 mgKOH / g, 90 mgKOH / g, 10 ... Examples of the hydroxyl value include H / g, 85 mgKOH / g, 80 mgKOH / g, 75 mgKOH / g, 70 mgKOH / g, 65 mgKOH / g, 60 mgKOH / g, 55 mgKOH / g, 50 mgKOH / g, 45 mgKOH / g, 44 mgKOH / g, 41 mgKOH / g, 40 mgKOH / g, 35 mgKOH / g, 30 mgKOH / g, 25 mgKOH / g, 22 mgKOH / g, 20 mgKOH / g, 15 mgKOH / g, 10 mgKOH / g, 5 mgKOH / g, and 4 mgKOH / g. In one embodiment, the hydroxyl value is preferably 4 mgKOH / g to 175 mgKOH / g, and more preferably 30 mgKOH / g to 175 mgKOH / g.

[0073] The hydroxyl value is measured by a method in accordance with JIS K0070 (neutralization titration method).

[0074] When the amount of monomer used in the production of a polymer can be accurately determined and the polymerization rate is high, the hydroxyl value can be calculated by the following formula. Hydroxyl value = [(weight of hydroxyl-containing monomer in 1 g of total monomer charge x number of hydroxyl groups per molecule of hydroxyl-containing monomer) / molecular weight of hydroxyl-containing monomer] x 56.11 (molecular weight of KOH) x 1000

[0075] Examples of the (meth)acrylic equivalent include 800g / eq, 775g / eq, 750g / eq, 725g / eq, 700g / eq, 675g / eq, 650g / eq, 625g / eq, 600g / eq, 500g / eq, 400g / eq, 300g / eq, 200g / eq, 150g / eq, 100g / eq, 50g / eq, and 0g / eq. In one embodiment, the (meth)acrylic equivalent is preferably less than 150g / eq, more preferably less than 100g / eq, and even more preferably 0g / eq. The reason for this preference is, for example, a reduction in curl (bending) of the cured product, compatibility between antiglare properties and mechanical properties, and the like.

[0076] "(Meth)acrylic equivalent" refers to the calculated mass per mole of (meth)acryloyl groups (g / eq).

[0077] Examples of weight average molecular weight: Mw (polymer) include 300,000, 290,000, 285,000, 284,000, 280,000, 250,000, 200,000, 175,000, 150,000, 140,000, 126,000, 125,000, 120,000, 110,000, 100,000, 90,000, 88,000, 80,000, 70,000, 65,000, 60,000, 50,000, 40,000, 37,500, 35,000, 30,000, 28,000, and 25,000. In one embodiment, the weight average molecular weight is preferably 25,000 to 300,000, more preferably 37,500 to 150,000, and even more preferably 50,000 to 100,000. The reason why it is preferable is, for example, improvement of leveling properties.

[0078] Examples of the number average molecular weight: Mn (polymer) include 60000, 55000, 54000, 50000, 45000, 40000, 35000, 30000, 28000, 27000, 25000, 23000, 21000, 20000, 19000, 17000, 15000, 14000, 12000, 10000, 9000, 8750, and 8500. In one embodiment, the number average molecular weight is preferably 8500 to 60000, more preferably 14000 to 35000, and even more preferably 15000 to 30000. The reason for this preference is, for example, improvement in leveling properties.

[0079] Molecular weight distribution: Mw / Mn (polymer) is, for example, 20, 19, 17, 15, 13, 11, 10, 9, 7, 5, 4.5, 4.2, 4, 3.5, 3, 2.5, 2.3, 2.1, etc. In one embodiment, the molecular weight distribution is preferably 2.1 to 20, more preferably 5 or less, and further preferably 2.5 to 4.2. The reason for this preference is, for example, improvement of leveling properties, etc.

[0080] The conditions for measuring the weight average molecular weight and the number average molecular weight are, for example, as follows. Measuring equipment: Tosoh Corporation, GPC (model number: HLC-8420) Column: Product name "TSKgel SuperHZM-M" (TOSOH) x 3 Eluent: Tetrahydrofuran Column temperature: 40℃ Calibration curve: Monodisperse polystyrene Detector: RI Polymer concentration: 1% by weight Measurement method: Measured after filtration.

[0081] (Manufacturing method (polymer)) The production method (polymer) may be, for example, radical polymerization.

[0082] The radical polymerization initiator may be used alone or in combination of two or more thereof. Examples of the radical polymerization initiator include inorganic peroxides, organic peroxides, and azo compounds.

[0083] Examples of inorganic peroxides include hydrogen peroxide, ammonium persulfate, and potassium persulfate.

[0084] Examples of the organic peroxide include benzoyl peroxide, dicumyl peroxide, and lauryl peroxide.

[0085] Examples of the azo compounds include 2,2'-azobisisobutyronitrile and dimethyl-2,2'-azobisisobutyrate.

[0086] The amount used in parts by mass (radical polymerization initiator / total monomer components) is preferably 0.1 parts by mass to 5 parts by mass.

[0087] In the preparation of the polymer, a chain transfer agent may be optionally used. The chain transfer agent may be used alone or in combination of two or more.

[0088] Examples of the chain transfer agent include lauryl mercaptan, dodecyl mercaptan, 2-mercaptobenzothiazole, bromotrichloromethane, and α-methylstyrene dimer.

[0089] The amount used in parts by mass (chain transfer agent / total monomer components) is preferably 0 to 5 parts by mass.

[0090] Examples of the mass% content (polymer / nonvolatile content of active energy ray-curable composition) include 20 mass%, 19 mass%, 17 mass%, 15 mass%, 13 mass%, 11 mass%, 10 mass%, 9 mass%, 7 mass%, 5 mass%, 3 mass%, 1 mass%, etc. In one embodiment, the content is preferably 1 mass% to 20 mass%.

[0091] In one embodiment, the content by weight [polymer / (urethane bond-free poly(meth)acrylate and urethane poly(meth)acrylate)] is preferably less than 50 parts by weight, more preferably 15 parts by weight or less. The reason why it is preferable is, for example, improvement of scratch resistance, improvement of pencil hardness, etc.

[0092] <Poly(meth)acrylate containing no urethane bonds> The urethane bond-free poly(meth)acrylates may be used alone or in combination of two or more kinds.

[0093] "Poly(meth)acrylate" means a compound having two or more (meth)acryloyl groups.

[0094] 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.

[0095] "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.

[0096] The number of (meth)acryloyl groups in the urethane bond-free 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 is preferably 2 to 20.

[0097] <(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 represents an integer of 0 to 2. b1’ ~R b6 ’ each independently represents a hydrogen atom, [ka] Represents. R b4’ and R b5’ may be different for each constituent unit. Formula (A ’ ) in [ka] Contains two or more. q represents an integer from 0 to 16. 1’ ~R 3 ’ R each independently represents a hydrogen atom or an alkyl group. 1’ may be different groups for each unit.

[0098] 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 Rb5A and R b5B This means that the group may be different from the group.

[0099] Examples of the pentaerythritol poly(meth)acrylate include pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, and pentaerythritol tetra(meth)acrylate.

[0100] 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).

[0101] Examples of the pentaerythritol polyepoxy modified (meth)acrylate include pentaerythritol diepoxy (meth)acrylate, pentaerythritol triepoxy (meth)acrylate, and pentaerythritol tetraepoxy (meth)acrylate.

[0102] 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.

[0103] 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).

[0104] 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.

[0105] <(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 represents an integer of 0 to 2. b7’ ~R b10 ’ each independently represents a hydrogen atom, [ka] Represents. R b9’ may be different for each constituent unit. Formula (B ’ ) in [ka] Contains two or more. q represents an integer from 0 to 16. 1’ ~R 3 ’R each independently represents a hydrogen atom or an alkyl group. 1’ may be different groups for each unit.

[0106] Examples of trimethylolpropane poly(meth)acrylate include trimethylolpropane di(meth)acrylate and trimethylolpropane tri(meth)acrylate.

[0107] 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).

[0108] Examples of trimethylolpropane polyepoxy modified (meth)acrylates include trimethylolpropane diepoxy (meth)acrylate and trimethylolpropane triepoxy (meth)acrylate.

[0109] Examples of polytrimethylolpropane poly(meth)acrylates include ditrimethylolpropane di(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, and ditrimethylolpropane tetra(meth)acrylate.

[0110] 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).

[0111] Examples of polytrimethylolpropane polyepoxy modified (meth)acrylates include ditrimethylolpropane diepoxy (meth)acrylate, ditrimethylolpropane triepoxy (meth)acrylate, and ditrimethylolpropane tetraepoxy (meth)acrylate.

[0112] <(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 represents an integer of 0 to 7. b11’ ~R b14 ’ each independently represents a hydrogen atom, [ka] Represents. R b13’ may be different for each constituent unit. Formula (C ’ ) in [ka] Contains two or more. q represents an integer from 0 to 16.1’ ~R 3 ’ R each independently represents a hydrogen atom or an alkyl group. 1’ may be different groups for each unit.

[0113] Examples of the glycerin poly(meth)acrylate include glycerin di(meth)acrylate and glycerin tri(meth)acrylate.

[0114] 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).

[0115] Examples of the glycerin polyepoxy modified (meth)acrylate include glycerin diepoxy (meth)acrylate and glycerin triepoxy (meth)acrylate.

[0116] 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.

[0117] 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.

[0118] 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.

[0119] <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, Rb15’ ~R b17 ’ each independently represents a hydrogen atom, [ka] It represents the formula (D ’ ) in [ka] Contains two or more. q represents an integer from 0 to 16. 1’ ~R 3 ’ R each independently represents a hydrogen atom or an alkyl group. 1’ may be different groups for each unit.

[0120] Examples of the isocyanurate structure-containing poly(meth)acrylate include isocyanuric acid di(meth)acrylate and isocyanuric acid tri(meth)acrylate.

[0121] 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).

[0122] Examples of the isocyanurate structure-containing polyepoxy-modified (meth)acrylate include isocyanuric acid diepoxy-modified (meth)acrylate and isocyanuric acid triepoxy-modified (meth)acrylate.

[0123] <(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] Represents R b20’ represents an alkylene group, and r represents an integer of 1 or greater. q represents an integer from 0 to 16. 1’ ~R 3 ’ R each independently represents a hydrogen atom or an alkyl group. 1’ may be different groups for each unit.

[0124] 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.

[0125] 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.

[0126] 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.

[0127] 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.

[0128] 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 di(ethylene oxide-modified (meth)acrylate), and tripropylene glycol di(ethylene oxide-modified (meth)acrylate).

[0129] 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.

[0130] <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] Represents. q represents an integer from 0 to 16. 1’ ~R 3 ’ R each independently represents a hydrogen atom or an alkyl group. 1’ may be different groups for each unit.

[0131] 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).

[0132] Examples of the hydroxyl value (poly(meth)acrylate not containing a urethane bond) include 100 mgKOH / g, 90 mgKOH / g, 80 mgKOH / g, 70 mgKOH / g, 60 mgKOH / g, 50 mgKOH / g, 40 mgKOH / g, 30 mgKOH / g, 20 mgKOH / g, 10 mgKOH / g, and 0 mgKOH / g. In one embodiment, the hydroxyl value is preferably 0 mgKOH / g to 100 mgKOH / g. The reason for this preference is, for example, improvement of antiglare properties.

[0133] Examples of the mass% content (urethane bond-free poly(meth)acrylate / active energy ray-curable composition nonvolatile content) include 90 mass%, 85 mass%, 81 mass%, 80 mass%, 78 mass%, 75 mass%, 70 mass%, 69 mass%, 68 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 90 mass%, and more preferably 50 mass% to 85 mass%.

[0134] <Urethane poly(meth)acrylate> The urethane poly(meth)acrylates may be used alone or in combination of two or more.

[0135] The number of (meth)acryloyl groups in the urethane 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 is preferably 2 to 20.

[0136] 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.

[0137] <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.

[0138] <Polyisocyanate> The polyisocyanates may be used alone or in combination of two or more.

[0139] "Polyisocyanate" means a compound that has two or more isocyanate groups (-N=C=O).

[0140] 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.

[0141] 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.

[0142] Examples of the branched aliphatic polyisocyanate include diethylpentylene diisocyanate, trimethylbutylene diisocyanate, trimethylpentylene diisocyanate, and trimethylhexamethylene diisocyanate.

[0143] Examples of the alicyclic polyisocyanate include monocyclic alicyclic polyisocyanates, crosslinked cyclic alicyclic polyisocyanates, and condensed cyclic alicyclic polyisocyanates.

[0144] 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.

[0145] Examples of the crosslinked alicyclic polyisocyanate include tricyclodecylene diisocyanate, adamantane diisocyanate, and norbornene diisocyanate.

[0146] An example of the condensed ring alicyclic polyisocyanate is bicyclodecylene diisocyanate.

[0147] Examples of the aromatic polyisocyanate include monocyclic aromatic polyisocyanates and condensed ring aromatic polyisocyanates.

[0148] 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 diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, and m-tetramethylxylylene diisocyanate.

[0149] An example of the condensed ring aromatic polyisocyanate is 1,5-naphthylene diisocyanate.

[0150] In one embodiment, the urethane poly(meth)acrylate is preferably a urethane poly(meth)acrylate having (poly)pentaerythritol poly(meth)acrylate as a constituent unit, more preferably a reaction product of (poly)pentaerythritol poly(meth)acrylate with an alicyclic polyisocyanate, or a reaction product of (poly)pentaerythritol poly(meth)acrylate with any of the nurate, biuret, or allophanate forms of a linear aliphatic polyisocyanate, and even more preferably a reaction product of (poly)pentaerythritol poly(meth)acrylate with isophorone diisocyanate, or a reaction product of (poly)pentaerythritol poly(meth)acrylate with hexamethylene diisocyanate.

[0151] Examples of the weight average molecular weight: Mw (urethane poly(meth)acrylate) include 30000, 20000, 15000, 10000, 9000, 8000, 7000, 6000, 5000, 4000, 3000, 2000, and 1500. In one embodiment, the weight average molecular weight is preferably 1500 to 30000, and more preferably 2000 to 20000. The reason for this preference is, for example, improvement in leveling properties.

[0152] Number average molecular weight: Mn (urethane poly(meth)acrylate) is, for example, 10000, 9000, 8000, 7000, 6000, 5000, 4000, 3000, 2000, 1200, 1000, etc. In one embodiment, the number average molecular weight is preferably 1000 to 10000, and more preferably 1200 to 8000. The reason for this preference is, for example, improvement in leveling properties, etc.

[0153] Molecular weight distribution: Mw / Mn (urethane poly(meth)acrylate) is, for example, 5, 4.5, 4, 3.5, 3, 2.5, 2.3, 2.1, 1.5, 1.4, 1.3, 1.1, 1.0, etc. In one embodiment, the molecular weight distribution is preferably 1.0 to 5, more preferably 4 or less, and even more preferably 3 or less. The reason for this being preferable is, for example, improvement of leveling properties, etc.

[0154] The measurement conditions for the weight average molecular weight (urethane poly(meth)acrylate) and the number average molecular weight (urethane poly(meth)acrylate) are, for example, the conditions described above.

[0155] Examples of the mass % content (urethane poly(meth)acrylate / non-volatile content of active energy ray-curable composition) include 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 %, etc. In one embodiment, the content is preferably 5 mass % to 65 mass %.

[0156] <particle> In one embodiment, the active energy ray-curable composition may optionally contain particles. The particles may be used alone or in combination of two or more kinds.

[0157] Examples of the particles include inorganic particles and organic particles.

[0158] (Inorganic particles) Examples of inorganic particles include metal oxide particles and silica particles.

[0159] Examples of the metal oxide particles include titanium oxide particles, zirconium oxide particles, niobium oxide particles, barium titanate particles, and zinc oxide particles.

[0160] In one embodiment, the particulate state is preferably a powder or a solvent-dispersed sol.

[0161] When the particles are in a solvent-dispersed sol state, the dispersion solvent is preferably an organic solvent.

[0162] The organic solvent may be used alone or in combination of two or more thereof. Examples of the organic solvent include the organic solvents described below.

[0163] (Meth)acryloyl group-containing inorganic particles In one embodiment, the inorganic particles are preferably (meth)acryloyl group-containing inorganic particles.

[0164] The (meth)acryloyl group-containing inorganic particles are a reaction product between inorganic particles and a (meth)acryloyl group-containing compound.

[0165] ((Meth)acryloyl group-containing compound) The (meth)acryloyl group-containing compounds may be used alone or in combination of two or more.

[0166] In one embodiment, the (meth)acryloyl group-containing compound includes a group represented by -XC(=Y)-NH-. (In the formula, X represents NH, O, or S. Y represents O or S.)

[0167] Examples of -XC(=Y)-NH- include -OC(=O)-NH-, -OC(=S)-NH-, -SC(=O)-NH-, -NH-C(=O)-NH-, -NH-C(=S)-NH-, and -SC(=S)-NH-. These groups may be used alone or in combination of two or more. In one embodiment, the above group is preferably -OC(=O)-NH-, -OC(=S)-NH-, or -SC(=O)-NH-. The reason for this preference is, for example, improvement in thermal stability.

[0168] The above group [-XC(=Y)-NH-] is believed to generate an appropriate cohesive force due to hydrogen bonds between molecules, and when the cured product is formed, it is believed to impart properties such as excellent mechanical strength, adhesion to the substrate, heat resistance, etc. Note that the above is merely one theory, and it is not intended that the present invention be restricted to the above theory.

[0169] Preferred examples of the (meth)acryloyl group-containing compound include a silanol group-containing compound and a silanol group-forming compound.

[0170] Examples of the silanol group-generating compound include compounds having an alkoxy group, an aryloxy group, an acetoxy group, an amino group, a halogen group, etc. on a silicon atom. In one embodiment, the silanol group-generating compound is preferably a compound containing an alkoxy group or an aryloxy group.

[0171] The silanol group or the silanol group-forming site of the silanol group-forming compound is a structural unit that bonds with the particles by a condensation reaction or a condensation reaction that occurs following hydrolysis.

[0172] In one embodiment, the (meth)acryloyl group-containing compound is preferably a compound represented by the following formula S. [ka] (In the formula, R s1 , R s2 R each independently represents a hydrogen atom, an alkyl group, or an aryl group. s3 R represents an alkylene group or an arylene group. s4 R represents a divalent organic group. s5 represents an organic group having a valence of (s''+1). Z represents a (meth)acryloyl group. s' represents an integer of 1 to 3. s'' represents an integer of 1 to 20.

[0173] In formula S, (R s1 O) s’ R s2 3-s’ Examples of Si- include a trimethoxysilyl group, a triethoxysilyl group, a triphenoxysilyl group, a methyldimethoxysilyl group, and a dimethylmethoxysilyl group. s1 O) s’ R s2 3-s’ Preferred examples of Si- include a trimethoxysilyl group and a triethoxysilyl group.

[0174] In formula S, R s4 R is, for example, an alkylene group, an arylene group, etc. s4 R may optionally contain elements other than carbon and hydrogen atoms. s4 may optionally contain a polyether linkage, a polyester linkage, a polyamide linkage, a polycarbonate linkage, -XC(=Y)-NH-. (In the formula, X represents NH, O, or S. Y represents O or S.)

[0175] Formula weight (R s4 ) is preferably 140,000 to 10,000, and more preferably 76 to 500.

[0176] In formula S, R s5R is, for example, an alkylene group, an arylene group, etc. s5 R may optionally contain elements other than carbon and hydrogen atoms. s5 may optionally contain a polyether linkage, a polyester linkage, a polyamide linkage, a polycarbonate linkage, -XC(=Y)-NH- (wherein X represents NH, O or S; Y represents O or S).

[0177] R s5 Examples of the group include the following groups. [ka] (s''' represents 0 to 2.)

[0178] In the formula S, s″ is preferably an integer of 1 to 20, more preferably an integer of 1 to 10, and even more preferably an integer of 1 to 5.

[0179] The (meth)acryloyl group-containing compound represented by formula S can be synthesized, for example, by the method described in JP-A-9-100111. The above synthesis method can be exemplified by the following method. Method (A): Addition reaction of mercaptoalkoxysilane, polyisocyanate, and active hydrogen group-containing (meth)acrylate Method (B): Reaction of a compound having an alkoxysilyl group and an isocyanate group with an active hydrogen-containing (meth)acrylate Method (C): Addition reaction of a compound having a (meth)acryloyl group and an isocyanate group with a mercaptoalkoxysilane or aminosilane

[0180] In one embodiment, the method for synthesizing the (meth)acryloyl group-containing compound represented by formula S is preferably the above-mentioned method (A). Examples of the above-mentioned method (A) include the following method. Method (A1): A method including a step of reacting a mercaptoalkoxysilane with a polyisocyanate to form an intermediate containing an alkoxysilyl group, an [-SC(=O)NH-] group, and an isocyanate group, and a step of reacting the intermediate with a hydroxyl group-containing (poly)(meth)acrylate to form an [-OC(=O)NH-] bond. Method (A2): A method including a step of reacting a polyisocyanate with a hydroxyl group-containing (poly)(meth)acrylate to form an intermediate containing a (meth)acryloyl group, an [-OC(=O)NH-] group, and an isocyanate group, and a step of reacting the intermediate with a mercaptoalkoxysilane to form a [-SC(=O)-NH-] bond. In one embodiment, method (A1) is preferred since there is no reduction in polymerizable unsaturated groups due to a Michael addition reaction.

[0181] The mercaptoalkoxysilanes may be used alone or in combination of two or more.

[0182] Examples of mercaptoalkoxysilanes include mercaptopropyltrimethoxysilane, mercaptopropyltriethoxysilane, mercaptopropylmethyldiethoxysilane, mercaptopropyldimethoxymethylsilane, mercaptopropylmethoxydimethylsilane, mercaptopropyltriphenoxysilane, and mercaptopropyltributoxysilane.

[0183] In one embodiment, the mercaptoalkoxysilane is preferably mercaptopropyltrimethoxysilane or mercaptopropyltriethoxysilane.

[0184] The polyisocyanate may be used alone or in combination of two or more thereof. Examples of the polyisocyanate include the compounds described below.

[0185] The hydroxyl group-containing (poly)(meth)acrylates may be used alone or in combination of two or more.

[0186] Examples of the hydroxyl group-containing (poly)(meth)acrylate include hydroxyl group-containing (meth)acrylate and hydroxyl group-containing poly(meth)acrylate.

[0187] Examples of hydroxyl group-containing (meth)acrylates include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, and 1,4-cyclohexanedimethanol mono(meth)acrylate.

[0188] Examples of the hydroxyl group-containing poly(meth)acrylate include the compounds described below.

[0189] In one embodiment, preferred examples of the hydroxyl group-containing poly(meth)acrylate include trimethylolpropane di(meth)acrylate, trimethylolethane di(meth)acrylate, pentaerythritol tri(meth)acrylate, and dipentaerythritol penta(meth)acrylate.

[0190] In one embodiment, preferred examples of the hydroxyl group-containing (poly)(meth)acrylate include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and pentaerythritol tri(meth)acrylate.

[0191] In one embodiment, the (meth)acryloyl group-containing compound does not contain a group represented by -XC(=Y)-NH-. (In the formula, X represents NH, O, or S. Y represents O or S.)

[0192] Examples of the (meth)acryloyl group-containing compound not containing a group represented by -XC(=Y)-NH- include compounds represented by formula U1. [ka] (In the formula, Z u R represents a (meth)acryloyl group. u1 R represents an alkylene group or an arylene group. u2 represents an alkyl group or an aryl group; and u represents 1 to 3.

[0193] Examples of the compound represented by formula U1 include tri(meth)acryloxyethyl monomethoxysilane, di(meth)acryloxyethyl dimethoxysilane, (meth)acryloxyethyl trimethoxysilane, tri(meth)acryloxypropyl monomethoxysilane, di(meth)acryloxypropyl dimethoxysilane, (meth)acryloxypropyl trimethoxysilane, tri(meth)acryloxypropyl monoethoxysilane, di(meth)acryloxypropyl diethoxysilane, (meth)acryloxypropyl triethoxysilane, tri(meth)acryloxypropyl monophenoxysilane, di(meth)acryloxypropyl diphenoxysilane, and (meth)acryloxypropyl triphenoxysilane.

[0194] Examples of the method for producing (meth)acryloyl group-containing inorganic particles include a method including a step of hydrolyzing alkoxysilane to obtain an alkoxysilane hydrolysate, a step of mixing the alkoxysilane hydrolysate with powdered silica particles or a solvent-dispersed sol of silica particles, and performing heating and stirring operations, a method of hydrolyzing alkoxysilane in the presence of particles, etc. In one embodiment, the method for producing ((meth)acryloyl group-containing inorganic particles) preferably includes a method of hydrolyzing alkoxysilane in the presence of particles.

[0195] The reaction temperature (production of (meth)acryloyl group-containing inorganic particles) is preferably 0°C to 150°C, and more preferably 20°C to 100°C.

[0196] The reaction time (production of (meth)acryloyl group-containing inorganic particles) is preferably 5 minutes to 24 hours.

[0197] In one embodiment, a dehydrating agent may be added to promote the reaction during the production of the (meth)acryloyl group-containing inorganic particles.

[0198] Examples of the dehydrating agent include inorganic dehydrating agents and organic dehydrating agents.

[0199] Examples of the inorganic dehydrating agent include zeolite, anhydrous silica, and anhydrous alumina.

[0200] Examples of the organic dehydrating agent include methyl orthoformate, ethyl orthoformate, tetraethoxymethane, and tetrabutoxymethane.

[0201] In one embodiment, the dehydrating agent is preferably an organic dehydrating agent, and more preferably, methyl orthoformate or ethyl orthoformate.

[0202] In one embodiment, the (meth)acryloyl group-containing inorganic particles contain a group represented by -XC(=Y)-NH-. (In the formula, X represents NH, O, or S. Y represents O or S.)

[0203] In one embodiment, the (meth)acryloyl group-containing inorganic particles do not contain a group represented by -XC(=Y)-NH-. (In the formula, X represents NH, O, or S. Y represents O or S.)

[0204] (organic particles) Examples of the organic particles include acrylic particles, styrene-acrylic particles, polystyrene particles, polyacrylonitrile particles, melamine particles, polyethylene particles, and benzoguanamine particles.

[0205] 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.

[0206] "A particles" refers to particles containing A resin as a raw material.

[0207] 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.).

[0208] 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.

[0209] Examples of commercially available products (polystyrene particles) include Techpolymer SBX-4 (manufactured by Sekisui Chemical Co., Ltd.), Chemisnow SX-130H, SX-350H, and SX-500H (manufactured by Soken Chemical Industries, Ltd.).

[0210] An example of a commercially available product (polyacrylonitrile particles) is Tuftic ASF (manufactured by Nippon Exlan Kogyo Co., Ltd.).

[0211] 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.).

[0212] 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.).

[0213] Examples of commercially available products (benzoguanamine particles) include Eposter MS, M05, and L15 (manufactured by Nippon Shokubai Co., Ltd.).

[0214] 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.

[0215] (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 it is preferable is, for example, hardness, flexibility, and the like.

[0216] Examples of particle diameters (organic particles) include 10 μm, 9.5 μm, 9 μm, 8.5 μm, 8 μm, 7.5 μm, 7 μm, 6.5 μm, 6 μm, 5.5 μm, 5 μm, 4.5 μm, 4 μm, 3.5 μm, 3 μm, 2.5 μm, 2 μm, 1.5 μm, 1 μm, and 0.5 μm. In one embodiment, the particle diameter is preferably 0.5 μm to 10 μm. The reason why this is preferable is, for example, improvement of antiglare properties.

[0217] "Particle size" refers to the volume average particle size. "Volume average particle size" refers to 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 using a dynamic light scattering method.

[0218] The volumetric particle size distribution can be measured by the following procedure. <Inorganic fine 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 Co., Ltd.) 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 <Organic fine particles> (1) Measurement of particle size distribution by volume Measuring equipment: "Microtrac MT3000II" (Microtrac BEL) Number of measurements: 2 Measurement temperature: room temperature Measurement time: 30 seconds Measurement upper limit: 1400μm Measurement lower limit: 0.2μm Measurement solvent: Refractive index of PGME: 1.404 The refractive index of the measurement sample (particles) can be referenced to literature values ​​("A GUIDE FOR ENTERING MICROTRAC "RUN INFORMATION" (F3) DATA", created by Leeds & Northrup).

[0219] Examples of the refractive index (inorganic particles) include 2.5, 2.3, 2.1, 2.0, 1.9, 1.7, 1.5, 1.3, 1.2, etc. In one embodiment, the refractive index is preferably 1.2 to 2.5.

[0220] Examples of the refractive index (organic particles) include 1.65, 1.63, 1.61, 1.60, 1.59, 1.57, 1.55, 1.53, 1.51, 1.50, and 1.49. In one embodiment, the refractive index is preferably 1.49 to 1.65.

[0221] The refractive index is measured under the following conditions. Standard: JIS K 7142(1996)

[0222] Examples of the particle shape include spherical, hollow, solid, porous, rod-like, plate-like, fibrous, and amorphous.

[0223] Examples of the particles include hydrophilic particles and hydrophobic particles.

[0224] Examples of the mass% content (particles / non-volatile content of active energy ray-curable composition) 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%, 5 mass%, 0 mass%, etc. In one embodiment, the content is preferably 0 mass% to 85 mass%, and more preferably 0 mass% to 40 mass%.

[0225] Examples of the mass% content (inorganic particles / nonvolatile content of active energy ray-curable composition) 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%, 5 mass%, 0 mass%, etc. In one embodiment, the content is preferably 0 mass% to 85 mass%, and more preferably 0 mass% to 40 mass%.

[0226] The mass % content (organic particles / nonvolatile content of active energy ray-curable composition) can be, for example, 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 30 mass %, and more preferably 0 mass % to 20 mass %.

[0227] <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.

[0228] 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.

[0229] 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.

[0230] Examples of α-hydroxycycloalkylphenones include 1-hydroxycyclohexyl phenyl ketone.

[0231] Examples of α-aminoalkylphenones include 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one.

[0232] An example of the benzyl dimethyl ketal is 2,2-dimethoxy-1,2-diphenylethan-1-one.

[0233] 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.

[0234] Examples of unsubstituted or substituted benzyl include benzyl and p-anisyl.

[0235] 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.

[0236] Examples of the acylphosphine oxide include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, and the like.

[0237] Examples of the substituted thioxanthone include 2-chlorothioxanthone, 2-isopropylthioxanthone, and 2,4-diethylthioxanthone.

[0238] 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).

[0239] When electron beam curing is used, a photoinitiator is not necessary.

[0240] 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 %.

[0241] <Polymerization inhibitor> In one embodiment, the active energy ray-curable composition may optionally contain a polymerization inhibitor. The polymerization inhibitor may be used alone or in combination of two or more kinds.

[0242] The polymerization inhibitor may, for example, be a hindered phenol.

[0243] The term "hindered phenol" refers to a compound having a "phenyl group having a tert-butyl group bonded to the carbon atom adjacent to the carbon atom having a phenolic hydroxyl group bonded thereto."

[0244] The hindered phenol may, for example, be a monohindered phenol.

[0245] The term "monohindered phenol" refers to a compound having one "phenyl group having a tert-butyl group bonded to the carbon atom adjacent to the carbon atom to which a phenolic hydroxyl group is bonded."

[0246] An example of the monohindered phenol is 2,6-di-tert-butyl-p-cresol.

[0247] In one embodiment, the polymerization inhibitor is preferably a hindered phenol, more preferably a monohindered phenol, and further preferably 2,6-di-tert-butyl-p-cresol. The reason for this preference is, for example, improvement in paint stability.

[0248] Examples of the mass% content (polymerization inhibitor / active energy ray curable composition non-volatile content) include 0.2 mass%, 0.19 mass%, 0.15 mass%, 0.13 mass%, 0.1 mass%, 0.09 mass%, 0.08 mass%, 0.07 mass%, 0.06 mass%, 0.05 mass%, 0.04 mass%, 0.03 mass%, 0.02 mass%, 0.01 mass%, 0 mass%, etc. In one embodiment, the content is preferably 0 mass% to 0.2 mass%, and more preferably 0.01 mass% to 0.2 mass%.

[0249] <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.

[0250] 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.

[0251] Examples of the ketone solvent include methyl ethyl ketone, acetylacetone, methyl isobutyl ketone, cyclopentanone, and cyclohexanone.

[0252] Examples of aromatic solvents include toluene and xylene.

[0253] Examples of the alcohol solvent include methanol, ethanol, n-propanol, isopropanol, n-butanol, i-butanol, and t-butanol.

[0254] Examples of the glycol solvent include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, polyethylene glycol, and polypropylene glycol.

[0255] 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.

[0256] Examples of the ester solvent include ethyl acetate, butyl acetate, methyl cellosolve acetate, ethyl cellosolve acetate, and propylene glycol monomethyl ether acetate.

[0257] Examples of the petroleum solvent include Solvesso #100 (manufactured by Exxon Corporation) and Solvesso #150 (manufactured by Exxon Corporation).

[0258] The haloalkane solvent may, for example, be chloroform.

[0259] The amide solvent may, for example, be dimethylformamide.

[0260] In one embodiment, the organic solvent is preferably an alcohol solvent, a glycol ether solvent, more preferably is isopropyl alcohol, n-butanol, isobutanol, propylene glycol monomethyl ether, more preferably is isopropyl alcohol and propylene glycol monomethyl ether in combination, n-butanol and propylene glycol monomethyl ether in combination, particularly preferably isopropyl alcohol and propylene glycol monomethyl ether in combination.The reason for preference is, for example, improvement of leveling property, etc.

[0261] 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%.

[0262] <Additives> The active energy ray-curable composition may optionally contain an agent (additive) that does not fall into any of the above categories.

[0263] Examples of the additives include ultraviolet absorbers, antifoaming agents, surface conditioners, antifouling agents, and pigments.

[0264] In one embodiment, the content in parts by mass (additive / active energy ray-curable composition) is 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, etc.

[0265] In one embodiment, the part by mass content (additive / polymer), the part by mass content (additive / poly(meth)acrylate not containing a urethane bond), and the part by mass content (additive / urethane poly(meth)acrylate) 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.

[0266] By dispersing and mixing the above-mentioned agents, an active energy ray-curable composition can be produced.

[0267] Examples of the dispersing and mixing means include an emulsifying disperser and an ultrasonic dispersing device.

[0268] Examples of uses (of the active energy ray-curable composition) include coating agents, hard coating agents, clear coating agents, clear hard coating agents, anti-glare coating agents, anti-glare hard coating agents, coating agents for optical films, and hard coating agents for optical films.

[0269] Specific examples of the active energy ray-curable composition include the following compositions. The numbers in the table represent parts by mass. The components in the table will be explained in the examples. [Table PEX1-1] [Table PEX1-2] [Table PEX1-3] [Table PEX2-1] [Table PEX2-2] [Table PEX2-3] [Table PEX2-4]

[0270] [Cured product] The present disclosure relates to a cured product of the above-mentioned active energy ray-curable composition.

[0271] The curing conditions are, for example, as follows:

[0272] [Laminate] The present disclosure relates to a laminate comprising the above-mentioned cured product.

[0273] 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

[0274] 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.

[0275] In one embodiment, the thickness (base material) is preferably 10 μm to 2000 μm.

[0276] In one embodiment, the thickness (of the cured layer) is preferably 0.05 μm to 20 μm.

[0277] (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 coater coating, offset printing, flexographic printing, and screen printing.

[0278] (Active energy ray curing process) Examples of the active energy rays include ultraviolet rays and electron beams.

[0279] Examples of ultraviolet light sources include a xenon lamp, a high-pressure mercury lamp, and a metal halide lamp.

[0280] 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

[0281] 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

[0282] 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.

[0283] Production Example 1-1: Polymer A four-neck flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, thermometer, and dropping funnel was charged with 0.5 parts of 2,2'-azobis(2-methylbutyronitrile) and 233 parts of propylene glycol monomethyl ether (PGME) as a polymerization initiator in a reaction vessel, and the monomers shown in the table below were added dropwise to the reaction vessel at 83°C for 2 hours. After 2 hours, 0.5 parts of 2,2'-azobis(2-methylbutyronitrile) was added and the reaction was continued for 3 hours to obtain a polymer (non-volatile content: 30%).

[0284] Unless otherwise stated, other examples were carried out in the same manner as above, except for the changes shown in the table below.

[0285] [Table 1] MMA: Methyl methacrylate HEMA: 2-hydroxyethyl methacrylate HEA: 2-hydroxyethyl acrylate Glass transition temperature: Calculated value (Fox formula) Hydroxyl value: Calculated value (formula given in the specification)

[0286] Comparative Manufacturing Example 1-1 A four-neck flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen inlet was charged with 125 parts of butyl acetate, 100 parts of glycidyl methacrylate (hereinafter, GMA), and 1 part of azobisisobutyronitrile (hereinafter, AIBN), and stirred. The mixture was heated to 85°C under a nitrogen stream and reacted for 10 hours. After the reaction was completed, the mixture was cooled to 60°C, and 50 parts of acrylic acid, 0.1 parts of triphenylphosphine, and 0.05 parts of methoquinone were charged. 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 reacted for 9 hours while keeping the temperature constant, to obtain a polymer (glass transition temperature: 12°C, number average molecular weight: 11000, weight average molecular weight: 32000, molecular weight distribution: 2.9, hydroxyl value: 262mgKOH / g).

[0287] In Comparative Production Example 1-1, the glass transition temperature was measured under the following conditions. Differential scanning calorimeter: Product name "DSC8230B", manufactured by Rigaku Corporation Heating rate: 10℃ / min

[0288] The weight average molecular weight, number average molecular weight, and molecular weight distribution were measured under the following conditions. Measuring equipment: Tosoh Corporation, GPC (model number: HLC-8420) Column: Product name "TSKgel SuperHZM-M" (Tosoh Corporation) x 3 Eluent: Tetrahydrofuran Column temperature: 40℃ Calibration curve: Monodisperse polystyrene Detector: RI Polymer concentration: 1% by weight Measurement method: Measured after filtration.

[0289] Production Example 2-1: Urethane poly(meth)acrylate The raw materials shown in the table below, including 0.05 parts of tin octoate, were charged into a reaction vessel equipped with a stirrer and a cooling tube, and the temperature inside the system was raised to about 80° C. over about 1 hour. The reaction system was then held at the same temperature for 2 hours and then cooled to obtain a urethane poly(meth)acrylate.

[0290] Unless otherwise stated, other examples were carried out in the same manner as above, except for the changes shown in the table below.

[0291] [Table 2] IPDI: Isophorone diisocyanate HDI Nurate: Nurate form of hexamethylene diisocyanate, product name "Coronate HXR", manufactured by Tosoh Corporation NK Ester A-9550: Dipentaerythritol polyacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd. Aronix M-305: Pentaerythritol polyacrylate, manufactured by Toagosei Co., Ltd. 4-HBA: 4-hydroxybutyl acrylate Measurement method (weight average molecular weight, number average molecular weight, molecular weight distribution): above conditions

[0292] 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 PGME to obtain an active energy ray-curable composition (non-volatile content: 30%).

[0293] Unless otherwise stated, other examples were carried out in the same manner as above, except for the changes shown in the table below.

[0294] [Table 3] [Table 4] NK Ester A-9550: Dipentaerythritol polyacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd. Aronix M-305: Pentaerythritol polyacrylate, manufactured by Toagosei Co., Ltd. Omnirad 184: 1-Hydroxycyclohexyl phenyl ketone, IGM Resins BHT: 2,6-di-tert-butyl-p-cresol

[0295] (Laminate) The active energy ray curable composition was applied to a substrate under the following conditions. The applied product was then dried under the following conditions. The dried product was then cured under the following conditions to obtain a laminate. Coating conditions Substrate: TAC film, product name "FT TD80UL", manufactured by Fujifilm Corporation Application method: Bar coater, model number "No.13", manufactured by RD SPECIALTIES Film thickness: approx. 5 μm Drying conditions 80℃ 1 minute (in a circulating air dryer) ·Curing conditions Irradiation distance: 20cm Belt speed: 5m / min Accumulative irradiation dose: 200mJ / cm2

[0296] (Pencil hardness test) Standard: JIS K5600-5-4(1999) Load: 500g

[0297] (Occurrence of bar stripes) The coating surface was visually observed for traces of bar coater unevenness. ○: No trace △: Slight traces ×: Clear traces present

[0298] (Occurrence of defects) The state of defects on the coating surface was visually observed. ○: No noticeable flaws △: Some defects are noticeable. ×: Defects are noticeable all over.

[0299] (Mandrel test) Standard: JIS K5600-5-1(1999) Measuring equipment: Cylindrical mandrel bending tester Measurement: The smallest diameter (mm) where no cracks or peeling are observed

[0300] Evaluation example Unless otherwise stated, the evaluation examples were carried out in the same manner as in the above examples, except for the changes shown in the table below.

[0301] [Table 5] ELCOM V-8804: Methacrylic modified silica particles, particle size: 12 nm, dispersion solvent: propylene glycol monomethyl ether, manufactured by JGC Catalysts and Chemicals Co., Ltd. SSX-102: Cross-linked polymethylmethacrylate particles, refractive index: 1.495, particle size: 2.5 μm, manufactured by Sekisui Plastics Co., Ltd. SSX-302ABE: Polystyrene particles, refractive index: 1.595, particle size: 2 μm, manufactured by Sekisui Plastics Co., Ltd.

[0302] (Uniformity of appearance) The uniformity of the appearance of the cured product was evaluated according to the following criteria. ○: Colorless and transparent ×: Whitening

[0303] (Hayes) Standard: JIS K 7136(2000) Measuring equipment: Haze meter, product name "HZ-V3", manufactured by Suga Test Instruments Co., Ltd.

[0304] (Glossiness) Standard: JIS Z 8741(1997) Measuring equipment: Gloss meter, product name "VG-7000", manufactured by Nippon Denshoku Industries Co., Ltd. Incident angle: 60°

Claims

1. An active energy ray-curable composition, The active energy ray-curable composition comprises a polymer, a urethane bond-free poly(meth)acrylate, and a urethane poly(meth)acrylate, The glass transition temperature of the polymer is 50° C. or higher. An active energy ray-curable composition.

2. The active energy ray-curable composition according to claim 1 , comprising particles.

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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