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

Abstract

[Problem] To provide an active energy ray-curable composition, a cured product, and a laminate. [Technical means] An active energy ray-curable composition which contains a polymer having a glass transition temperature of 50 DEG C or higher, a poly (meth) acrylate that does not contain urethane bonds, and a urethane poly (meth) acrylate.

Description

Technical Field

[0001] The present disclosure relates to an active energy ray-curable composition, a cured product, and a laminate. Background Art

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

[0003] [Patent Document 1] Japanese Patent Publication No. 62-021815 Summary of the invention [Technical problem to be solved by the invention]

[0004] The problem to be solved by the present invention is to provide an active energy ray-curable composition which can produce a cured product having good hardness and bendability and has good coating properties. [Technical means to solve technical problems]

[0005] According to the present disclosure, the following items are provided. (Item 1) An active energy ray-curable composition, comprising: a polymer, a poly(meth)acrylate not containing a urethane bond, and a urethane poly(meth)acrylate. The glass transition temperature of the polymer is 50° C. or higher. (Item 2) The active energy ray-curable composition according to the above item includes 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 in the above item.

[0006] In the present disclosure, one or more features may be provided in further combinations than those explicitly shown. [Beneficial Effects]

[0007] The active energy ray-curable composition of the present invention exhibits good coating properties. In addition, the cured product of the present invention exhibits good hardness and bendability. DETAILED DESCRIPTION

[0008] In the whole of the present disclosure, the range of the numerical values ​​of each physical property value, content, etc. can be set appropriately (for example, selected from the values ​​described in the following items). Specifically, with respect to the numerical value α, when A3, A2, A1 (set as A3>A2>A1) and the like are cited, the range of the numerical value α can be listed as less than A3, less than A2, less than A3, less than A2, more than A1, more than A2, greater than A1, greater than A2, A1-A2 (more than A1 and less than A2), A1-A3, A2-A3, more than A1 and less than A3, more than A1 and less than A2, more 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, 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 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 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 less than A3, greater than A1 and less than A2, greater than A2 and less than A3, greater than A3 and less than A3, greater than A1 and less than A2, greater than A2 and less than A3, etc.

[0009] As long as the problems to be solved by the present invention are solved, the components, conditions, numerical values ​​and the like are not particularly limited.

[0010] "αβ amount (A / B)" refers to the β amount (α) of A relative to B100α. Examples of α include mass %, mole %, and mass parts. Examples of β amount include content and usage amount. "Mass % content (A / B)" refers to the content (mass %) of A relative to B100 mass %.

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

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

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

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

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

[0016] The "branched alkyl group" refers to a group in which at least one hydrogen atom of a linear alkyl group is substituted with an alkyl group and the group does not have a ring structure.

[0017] Examples of the branched alkyl group include isopropyl, diethylpentyl, trimethylbutyl, trimethylpentyl, and trimethylhexyl.

[0018] Examples of the cycloalkyl group include a monocyclic cycloalkyl group, a bridged ring cycloalkyl group, a condensed ring cycloalkyl group, etc. Furthermore, a group in which at least one hydrogen atom of a cycloalkyl group is substituted by an alkyl group is also considered to be a cycloalkyl group.

[0019] "Single ring" refers to a ring structure formed by covalent bonds of carbon without a bridging structure inside. "Fused ring" refers to a ring structure in which two or more single rings share two atoms (i.e., only one side of each ring is shared (fused) with each other). "Bridged ring" refers to a ring structure in which two or more single rings share three or more atoms.

[0020] Examples of the monocyclic cycloalkyl group include cyclopentyl, cyclohexyl, cycloheptyl, cyclodecyl, and 3,5,5-trimethylcyclohexyl.

[0021] Examples of the bridged cycloalkyl group include tricyclodecanyl, adamantyl, and norbornyl.

[0022] In addition, the alkyl group also includes a group in which a linear alkyl group, a branched alkyl group, and a cycloalkyl group are combined. Examples of such a group in which a linear alkyl group, a branched alkyl group, and a cycloalkyl group are combined include a cycloalkylalkyl group and the like.

[0023] The cycloalkylalkyl group is represented by the following formula. R calkyl -R alkyl - (Where R calkyl represents a cycloalkyl group. alkyl represents an alkyl group. )

[0024] Examples of the alkylene group include a linear alkylene group, a branched alkylene group, and a cycloalkylene group.

[0025] Examples of the linear alkylene group include methylene, ethylene, n-propylene, n-butylene, n-pentylene, n-hexylene, n-heptylene, n-octylene, n-nonylene, and n-decylene.

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

[0027] Examples of the cycloalkylene group include monocyclic cycloalkylene groups, bridged cycloalkylene groups, condensed cycloalkylene groups, etc. Furthermore, one or more hydrogen atoms of the cycloalkylene group may be substituted with a linear or branched alkyl group.

[0028] Examples of the monocyclic cycloalkylene group include cyclopentylene, cyclohexylene, cycloheptylene, cyclodecylene, and 3,5,5-trimethylcyclohexylene.

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

[0030] Examples of the fused ring cycloalkylene group include bicyclodecanylene and the like.

[0031] In addition, the alkylene group also includes a group in which a linear alkylene group, a branched alkylene group, and a cycloalkylene group are combined. Examples of such a group include a cycloalkylene alkylene group and an alkylene cycloalkylene alkylene group.

[0032] The cycloalkylenealkylene group is represented by the following formula. -R calkylene -R alkylene - (Where 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 - (Where 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 phenyl, tolyl, and mesityl.

[0037] Examples of the fused ring aryl group include naphthyl and the like.

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

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

[0040] Examples of the fused ring arylene group include naphthylene and the like.

[0041] [Active energy ray-curable composition] The present disclosure relates to an active energy ray-curable composition, comprising: a polymer, a poly(meth)acrylate not containing a urethane bond, and a urethane poly(meth)acrylate, wherein the glass transition temperature of the polymer is 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 contain a non-polar monomer unit. The non-polar monomer may be used alone or in combination of two or more.

[0044] Examples of the non-polar monomer include unsubstituted alkyl (meth)acrylates and alkenyl aryl compounds.

[0045] Examples of the unsubstituted alkyl (meth)acrylate include unsubstituted linear alkyl (meth)acrylate, unsubstituted branched alkyl (meth)acrylate, and unsubstituted alicyclic alkyl (meth)acrylate.

[0046] Examples of the unsubstituted straight-chain alkyl (meth)acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, n-pentyl (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, palmitate (meth)acrylate, heptadecyl (meth)acrylate, and stearate (meth)acrylate.

[0047] Examples of the unsubstituted branched alkyl (meth)acrylate include isopropyl (meth)acrylate, isobutyl (meth)acrylate, isoamyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate.

[0048] As unsubstituted alicyclic alkyl (meth)acrylate, cyclohexyl (meth)acrylate etc. are mentioned, for example.

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

[0050] The mass % content (non-polar monomer unit / polymer) includes, for example, 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 further preferably 65 mass % to 95 mass %.

[0051] The mole % content (non-polar monomer unit / polymer) includes, for example, 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%, 0 mol%, etc. In one embodiment, the content preferably includes 0 mol% to 99 mol%, more preferably 50 mol% to 99 mol%, and further preferably 65 mol% to 96 mol%. The preferred reasons include, for example, improved leveling and improved compatibility.

[0052] (Hydroxy-containing monomer unit) The polymer may contain a hydroxyl group-containing monomer unit. The hydroxyl group-containing monomer may be used alone or in combination of two or more.

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

[0054] Examples of the hydroxyl group-containing (meth)acrylate include hydroxyl group-containing linear (meth)acrylate and hydroxyl group-containing branched (meth)acrylate.

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

[0056] Examples of the hydroxyl-containing branched (meth)acrylate 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-methyl-propyl (meth)acrylate, 2-hydroxy-1-methyl-propyl (meth)acrylate, 3-hydroxy-1-methyl-propyl (meth)acrylate, 1-ethyl-2-hydroxyethyl (meth)acrylate, 1-hydroxy-2-methyl-propyl (meth)acrylate, 2-hydroxy-2-methyl-propyl (meth)acrylate, 3-hydroxy-2-methyl-propyl (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 hydroxy linear alkyl vinyl ether, hydroxy branched alkyl vinyl ether, and hydroxy cycloalkyl 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] The mass % content (hydroxyl-containing monomer units / polymer) includes, for example, 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 further preferably 5 mass % to 30 mass %.

[0061] The mole % content (hydroxyl-containing monomer units / polymer) includes, for example, 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%. The reasons for this are, for example, improved leveling and improved compatibility.

[0062] (Other structural units) 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 the above monomers include (meth)acrylic acid, (meth)acrylamide, (meth)acrylonitrile, and polyfunctional (meth)acrylate.

[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] Examples of the mass % content (other structural units / non-polar monomer units, hydroxyl-containing monomer units, and any one of the hydroxyl-containing structural units) 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 %.

[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] Examples of the mole % content (other structural units / non-polar monomer units, hydroxyl-containing monomer units, and any one of the hydroxyl-containing structural units) 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 %.

[0069] <Physical properties, etc. (polymer)> The glass transition temperature (polymer) includes, for example, 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, 50°C, etc. In one embodiment, the glass transition temperature of the component (A) is preferably 50°C to 190°C, more preferably 90°C to 190°C.

[0070] The glass transition temperature is measured by the following conditions. Differential Scanning Calorimeter: Product name: "DSC8230B", manufactured by Rigaku Electric Co., Ltd. Heating rate: 10℃ / min

[0071] When the input amount of the monomers used in producing the polymer can be accurately known and the polymerization rate is high, the glass transition temperature can be calculated by Fox's equation. Fox's formula: 1 / Tg = (Wa / Tga) + (Wb / Tgb) + ... + (Wn / Tgn) Tg: glass transition temperature of copolymer (K) Wa: mass % of monomer A Tga: Glass transition temperature of the homopolymer of monomer A (K) Wb: mass % of monomer B Tgb: Glass transition temperature of the homopolymer of monomer B (K) Wn: mass % of monomer N Tgn: Glass transition temperature of the 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 OH / g, 85mgKOH / g, 80mgKOH / g, 75mgKOH / g, 70mgKOH / g, 65mgKOH / g, 60mgKOH / g, 55mgKOH / g, 50mgKOH / g, 45mgKOH / g, 44mgKOH / g, 41mgKOH / g, 40mgKOH / g, 35mgKOH / g, 30mgKOH / g, 25mgKOH / g, 22mgKOH / g, 20mgKOH / g, 15mgKOH / g, 10mgKOH / g, 5mgKOH / g, 4mgKOH / g, etc. In one embodiment, the hydroxyl value is preferably 4mgKOH / g to 175mgKOH / g, more preferably 30mgKOH / g to 175mgKOH / g.

[0073] The hydroxyl value can be measured by a method in accordance with Japanese Industrial Standard (JIS) K0070 (neutralization titration method).

[0074] When the input amount of the monomers used in producing the polymer can be accurately known and the polymerization rate is high, the hydroxyl value can be calculated by the following formula. Hydroxyl value = [(the input mass of the hydroxyl-containing monomer in 1 g of the total input monomers × the number of hydroxyl groups in one molecule of the hydroxyl-containing monomer) / molecular weight of the hydroxyl-containing monomer] × 56.11 (molecular weight of KOH) × 1000

[0075] The (meth) acrylic acid equivalent, for example, includes 800 g / eq, 775 g / eq, 750 g / eq, 725 g / eq, 700 g / eq, 675 g / eq, 650 g / eq, 625 g / eq, 600 g / eq, 500 g / eq, 400 g / eq, 300 g / eq, 200 g / eq, 150 g / eq, 100 g / eq, 50 g / eq, 0 g / eq, etc. In one embodiment, the (meth) acrylic acid equivalent is preferably less than 150 g / eq, more preferably less than 100 g / eq, and further preferably 0 g / eq. The preferred reasons include, for example, reducing the curling (bending) of the cured product, while achieving anti-glare performance and mechanical properties.

[0076] The "(meth)acrylic acid equivalent" refers to a calculated value (g / eq) of the mass per 1 mol of the (meth)acryloyl group.

[0077] Weight average molecular weight: Mw (polymer) includes, for example, 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 25000 to 300000, more preferably 37500 to 150000, and even more preferably 50000 to 100000. The reason for this preference is, for example, improvement in leveling properties.

[0078] Number average molecular weight: Mn (polymer) includes, for example, 60000, 55000, 54000, 50000, 45000, 40000, 35000, 30000, 28000, 27000, 25000, 23000, 21000, 20000, 19000, 17000, 15000, 14000, 12000, 10000, 9000, 8750, 8500, etc. In one embodiment, the number average molecular weight is preferably 8500 to 60000, more preferably 14000 to 35000, and further preferably 15000 to 30000. The preferred reason is, for example, improved leveling properties.

[0079] Molecular weight distribution: Mw / Mn (polymer) includes, 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 is, for example, improved leveling properties.

[0080] Examples of the measurement conditions for the weight average molecular weight and the number average molecular weight include the following conditions. ·Measurement equipment: GPC (model: HLC-8420) manufactured by Tosoh Corporation Column: Product name "TSKgel SuperHZM-M" (TOSOH) × 3 ·Eluent: Tetrahydrofuran Column temperature: 40°C Calibration curve: monodisperse polystyrene Detector: refractive index (RI) ·Polymer concentration: 1 mass% ·Measurement method: Measure after filtering.

[0081] (Production Method (Polymer)) Examples of the production method (polymer) include radical polymerization.

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

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

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

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

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

[0087] In the production 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 / active energy ray-curable composition non-volatile component) 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 [polymer / (poly(meth)acrylate not containing urethane bonds and urethane poly(meth)acrylate)] is preferably less than 50 parts by mass, and more preferably 15 parts by mass or less. The reasons for this are, for example, improved scratch resistance and improved pencil hardness.

[0092] <Poly (meth)acrylates not containing urethane bonds> The poly(meth)acrylates not containing a urethane bond may be used alone or in combination of two or more.

[0093] The "poly (meth)acrylate" refers to a compound having two or more (meth)acryloyl groups.

[0094] Examples of poly(meth)acrylates not containing a urethane bond include (poly)pentaerythritol poly(alkylene oxide-modified or epoxy-modified) (meth)acrylate, (poly)trimethylolpropane poly(alkylene oxide-modified or epoxy-modified) (meth)acrylate, (poly)glycerol 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] The “poly(alkylene oxide-modified or epoxy-modified) (meth)acrylate” refers to one or more selected from the group consisting of poly(meth)acrylate, polyalkylene oxide-modified (meth)acrylate and polyepoxy-modified (meth)acrylate.

[0096] Examples of the number of (meth)acryloyl groups in the poly(meth)acrylate not containing a urethane bond include 20, 19, 18, 17, 16, 15, 14, 13, 12, 11, 10, 9, 8, 7, 6, 5, 4, 3, and 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.

Chemical A1

Chemical A2

[0098] In addition, "the groups may be different for each structural unit" means that in formula (A'), for example, when n is 2,

Chemical A4

[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 the pentaerythritol polyalkylene oxide-modified (meth)acrylate 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 the polypentaerythritol poly(meth)acrylate 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 hexa(meth)acrylate, tripentaerythritol hepta(meth)acrylate and tripentaerythritol octa(meth)acrylate.

[0103] Examples of the polypentaerythritol polyalkylene oxide-modified (meth)acrylate 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(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), (meth)acrylate), tripentaerythritol tetra(ethylene oxide modified (meth)acrylate), tripentaerythritol penta(ethylene oxide modified (meth)acrylate), tripentaerythritol hexa(ethylene oxide modified (meth)acrylate), tripentaerythritol heptath(ethylene oxide modified (meth)acrylate), tripentaerythritol octa(ethylene oxide modified (meth)acrylate), tripentaerythritol di(propylene oxide modified (meth)acrylate), tripentaerythritol 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 heptath(propylene oxide modified (meth)acrylate), tripentaerythritol octa(propylene oxide modified (meth)acrylate), and the like.

[0104] Examples of the polypentaerythritol polyepoxy-modified (meth)acrylate include dipentaerythritol diepoxy (meth)acrylate, dipentaerythritol triepoxy (meth)acrylate, dipentaerythritol tetraepoxy (meth)acrylate, dipentaerythritol pentaepoxy (meth)acrylate, dipentaerythritol hexaepoxy (meth)acrylate, tripentaerythritol diepoxy (meth)acrylate, tripentaerythritol triepoxy (meth)acrylate, tripentaerythritol tetraepoxy (meth)acrylate, tripentaerythritol pentaepoxy (meth)acrylate, tripentaerythritol hexaepoxy (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 the formula (B′) or the like.

Chemical B1

Chemical B2

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

[0107] Examples of the trimethylolpropane polyalkylene oxide-modified (meth)acrylate 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 the trimethylolpropane polyepoxy-modified (meth)acrylate include trimethylolpropane diepoxy (meth)acrylate and trimethylolpropane triepoxy (meth)acrylate.

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

[0110] Examples of the polytrimethylolpropane polyalkylene oxide-modified (meth)acrylate include di-trimethylolpropane di(ethylene oxide-modified (meth)acrylate), di-trimethylolpropane tri(ethylene oxide-modified (meth)acrylate), di-trimethylolpropane tetra(ethylene oxide-modified (meth)acrylate), di-trimethylolpropane di(propylene oxide-modified (meth)acrylate), di-trimethylolpropane tri(propylene oxide-modified (meth)acrylate), and di-trimethylolpropane tetra(propylene oxide-modified (meth)acrylate).

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

[0112] <(Poly)glycerol poly(alkylene oxide modified or epoxy modified) (meth)acrylate> (Poly)glycerol poly(alkylene oxide-modified or epoxy-modified) (meth)acrylate is a compound represented by formula (C′) or the like.

Chemical C1

Chemical C2

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

[0114] Examples of the glycerol polyalkylene oxide-modified (meth)acrylate include glycerol di(ethylene oxide-modified (meth)acrylate), glycerol tri(ethylene oxide-modified (meth)acrylate), glycerol di(propylene oxide-modified (meth)acrylate), and glycerol 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 the polyglycerol poly(meth)acrylate 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 the polyglycerol polyalkylene oxide-modified (meth)acrylate 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), diglycerol di(propylene oxide-modified (meth)acrylate), diglycerol tri(propylene oxide-modified (meth)acrylate), diglycerol tetra(propylene oxide-modified (meth)acrylate), triglycerol di(propylene oxide-modified (meth)acrylate), triglycerol tri(propylene oxide-modified (meth)acrylate), triglycerol tetra(propylene oxide-modified (meth)acrylate), triglycerol penta(propylene oxide-modified (meth)acrylate), and the like.

[0118] Examples of the polyglycerol polyepoxy-modified (meth)acrylate 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] <Poly(alkylene oxide-modified or epoxy-modified) (meth)acrylate containing isocyanurate structure> The poly(alkylene oxide-modified or epoxy-modified) (meth)acrylate containing an isocyanurate structure is a compound represented by the formula (D′) or the like.

Chemical D1

Chemical D 2

[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 polyalkylene oxide-modified (meth)acrylate containing an isocyanurate structure 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 isocyanurate diepoxy-modified (meth)acrylate and isocyanurate triepoxy-modified (meth)acrylate.

[0123] <(Poly)alkylene di(alkylene oxide-modified or epoxy-modified) (meth)acrylate> (Poly)alkylene di(alkylene oxide-modified or epoxy-modified) (meth)acrylate is a compound represented by formula (E') or the like.

Chemical E1

Chemical E2

[0124] Examples of the alkylene di(meth)acrylate include 1,2-ethylene glycol di(meth)acrylate, 1,3-propylene glycol di(meth)acrylate, 1,4-butylene glycol 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-ethylene glycol di(ethylene oxide-modified (meth)acrylate), 1,3-propylene glycol di(ethylene oxide-modified (meth)acrylate), 1,4-butylene glycol 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), and 1,6-hexanediol di(ethylene oxide-modified (meth)acrylate). (meth)acrylate), 1,2-ethylene glycol di(propylene oxide modified (meth)acrylate), 1,3-propylene glycol di(propylene oxide modified (meth)acrylate), 1,4-butylene glycol 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), etc.

[0126] Examples of the alkylene diepoxy-modified (meth)acrylate include 1,2-ethylene glycol diepoxy (meth)acrylate, 1,3-propylene glycol diepoxy (meth)acrylate, 1,4-butylene glycol 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 the polyalkylene dialkylene oxide-modified (meth)acrylate 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.

Chemistry F1

Chemistry F2

[0131] Examples of the bisphenol A dialkylene oxide-modified (meth)acrylate include bisphenol A di(ethylene oxide-modified (meth)acrylate) and bisphenol A di(propylene oxide-modified (meth)acrylate).

[0132] The hydroxyl value (poly (meth) acrylate without urethane bond) includes, for example, 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, 0 mgKOH / g, etc. In one embodiment, the hydroxyl value is preferably 0 mgKOH / g to 100 mgKOH / g. The preferred reason is, for example, improved anti-glare performance.

[0133] The mass % content (poly (meth) acrylate not containing urethane bonds / active energy ray curable composition non-volatile component) includes, for example, 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 %, 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] Examples of the number of (meth)acryloyl groups in the urethane poly(meth)acrylate include 20, 19, 18, 17, 16, 15, 14, 13, 12, 11, 10, 9, 8, 7, 6, 5, 4, 3, and 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 consisting of a hydroxyl group-containing poly(meth)acrylate and a polyisocyanate.

[0137] <Hydryl-containing poly(meth)acrylate> Examples of the hydroxyl-containing poly(meth)acrylate include hydroxyl-containing pentaerythritol poly(meth)acrylate, hydroxyl-containing (poly)trimethylolpropane poly(meth)acrylate, and hydroxyl-containing (poly)glycerol poly(meth)acrylate.

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

[0139] “Polyisocyanate” refers to a compound having two or more isocyanate groups (—N═C═O).

[0140] Examples of the polyisocyanate include linear aliphatic polyisocyanate, branched aliphatic polyisocyanate, alicyclic polyisocyanate, aromatic polyisocyanate, and biuret forms, isocyanurate forms, allophanate forms, and adduct forms 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 polyisocyanate, bridged alicyclic polyisocyanate, and condensed alicyclic polyisocyanate.

[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 bridged alicyclic polyisocyanate include tricyclodecylene diisocyanate, adamantane diisocyanate, and norbornene diisocyanate.

[0146] Examples of the condensed-ring alicyclic polyisocyanate include bicyclodecylene diisocyanate and the like.

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

[0148] Examples of the monocyclic aromatic polyisocyanate include dialkyldiphenylmethane diisocyanates such as 4,4'-diphenyldimethylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanates such as 4,4'-diphenyltetramethylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-dibenzyl diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, toluene diisocyanate, xylylene diisocyanate, and tetramethyl-m-xylylene diisocyanate.

[0149] Examples of the condensed ring aromatic polyisocyanate include 1,5-naphthalene diisocyanate and the like.

[0150] In one embodiment, the urethane poly(meth)acrylate preferably includes a urethane poly(meth)acrylate having a (poly)pentaerythritol poly(meth)acrylate in a structural unit, more preferably includes a reaction product of (poly)pentaerythritol poly(meth)acrylate and an alicyclic polyisocyanate, a reaction product of (poly)pentaerythritol poly(meth)acrylate and any one of a urate form, a biuret form, and an allophanate form of a linear aliphatic polyisocyanate, and further preferably includes a reaction product of (poly)pentaerythritol poly(meth)acrylate and isophorone diisocyanate, a reaction product of (poly)pentaerythritol poly(meth)acrylate and a urate form of hexamethylene diisocyanate.

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

[0152] Number average molecular weight: Mn (urethane poly (meth) acrylate) includes, 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, more preferably 1200 to 8000. The reason for this is, for example, improvement in leveling properties.

[0153] Molecular weight distribution: Mw / Mn (urethane poly(meth)acrylate) includes, 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 further preferably 3 or less. The reason for this is, for example, improved leveling properties.

[0154] Examples of the measurement conditions of the weight average molecular weight (urethane poly(meth)acrylate) and the number average molecular weight (urethane poly(meth)acrylate) include the above-mentioned conditions.

[0155] The mass % content (urethane multi (meth) acrylate / active energy ray curable composition non-volatile component) includes, for example, 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] <Particles> In one embodiment, the active energy ray-curable composition may optionally include particles. The particles may be used alone or in combination of two or more.

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

[0158] (Inorganic particles) Examples of the 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 particle state is preferably powder or solvent-dispersed sol.

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

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

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

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

[0165] ((Meth)acryloyl group-containing compound) The (meth)acryloyl group-containing compound 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 -X-C(=Y)-NH-. (In the formula, X represents NH, O or S. Y represents O or S.)

[0167] -X-C(=Y)-NH- includes, for example, -O-C(=O)-NH-, -O-C(=S)-NH-, -S-C(=O)-NH-, -NH-C(=O)-NH-, -NH-C(=S)-NH-, -S-C(=S)-NH-, etc. These groups may be used alone or in combination of two or more. In one embodiment, the group preferably includes -O-C(=O)-NH-, -O-C(=S)-NH-, and -S-C(=O)-NH-. The preferred reason is, for example, improved thermal stability.

[0168] It is believed that the group [-XC(=Y)-NH-] generates moderate cohesive force through hydrogen bonding between molecules, and when forming a cured product, it imparts excellent mechanical strength, adhesion to a substrate, heat resistance, and other properties. In addition, the above is only one statement, and the present invention is not intended to be limited by the above statement.

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

[0170] Examples of the silanol group-forming 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-forming compound preferably includes an alkoxy group- or aryloxy group-containing compound.

[0171] The silanol group or the silanol group-forming site of the compound that generates a silanol group is a structural unit that bonds to the particle through a condensation reaction or a condensation reaction that occurs after hydrolysis.

[0172] In one embodiment, as the (meth)acryloyl group-containing compound, preferably a compound represented by the following formula S is used.

Chemistry S

[0173] In formula S, (R s1 O) s’ R s2 3－s’ Si- includes, for example, trimethoxysilyl, triethoxysilyl, triphenoxysilyl, methyldimethoxysilyl, dimethylmethoxysilyl, and the like. In one embodiment, (Rs1 O) s’ R s2 3－s’ Preferred examples of Si- include trimethoxysilyl and triethoxysilyl.

[0174] In formula S, R s4 For example, alkylene group, arylene group, etc. are mentioned. s4 Elements other than carbon atoms and hydrogen atoms may be optionally contained. s4 Optionally, it may contain a polyether bond, a polyester bond, a polyamide bond, a polycarbonate bond, or -X-C(=Y)-NH-. (In the formula, X represents NH, O or S. Y represents O or S.)

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

[0176] In formula S, R s5 For example, alkylene group, arylene group, etc. are mentioned. s5 Elements other than carbon atoms and hydrogen atoms may be optionally contained. s5 It may optionally contain a polyether bond, a polyester bond, a polyamide bond, a polycarbonate bond, or -X-C(=Y)-NH- (wherein X represents NH, O or S, and Y represents O or S).

[0177] R s5 For example, the following groups etc. are mentioned.

Chemical S2

[0178] In the formula S, s" is preferably 1-20, more preferably 1-10, and even more preferably 1-5.

[0179] Examples of the synthesis method of the (meth)acryloyl group-containing compound represented by Formula S include the method described in Japanese Patent Application Laid-Open No. 9-100111. Examples of the synthesis method include the following method. Method (A): Addition reaction of mercaptoalkoxysilane with polyisocyanate and (meth)acrylate containing active hydrogen group (B) Method: Reaction of a compound having an alkoxysilyl group and an isocyanate group with a (meth)acrylate containing an active hydrogen group Method (C): Addition reaction of a compound having a (meth)acryloyl group and an isocyanate group with mercaptoalkoxysilane or aminosilane

[0180] In one embodiment, the method for synthesizing the (meth)acryloyl group-containing compound represented by Formula S is preferably the method (A). The method (A) includes, for example, the following method. Method (A1) is a method comprising the following steps: firstly reacting mercaptoalkoxysilane with polyisocyanate to form an intermediate containing an alkoxysilyl group, a [—SC(═O)NH—] group and an isocyanate group; and reacting the intermediate with a hydroxyl-containing (poly) (meth)acrylate to form a [—OC(═O)NH—] bond. Method (A2) is a method comprising the following steps: firstly reacting a polyisocyanate with a hydroxyl-containing (poly) (meth) acrylate to form an intermediate containing a (meth) acryloyl group, a [—OC(═O)NH—] group and an isocyanate group; and reacting a mercaptoalkoxysilane with the intermediate to form a [—SC(═O)—NH—] bond. In one embodiment, method (A1) is preferred from the viewpoint that the polymerizable unsaturated group does not decrease due to the Michael addition reaction.

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

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

[0183] In one embodiment, the mercaptoalkoxysilane preferably includes mercaptopropyltrimethoxysilane and mercaptopropyltriethoxysilane.

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

[0185] The hydroxyl group-containing (poly)(meth)acrylate 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 the hydroxyl group-containing (meth)acrylate 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, the hydroxyl group-containing poly(meth)acrylate preferably includes trimethylolpropane di(meth)acrylate, trimethylolethane di(meth)acrylate, pentaerythritol tri(meth)acrylate, and dipentaerythritol penta(meth)acrylate.

[0190] In one embodiment, the hydroxyl group-containing (poly) (meth)acrylate preferably includes 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 -X-C(=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 that does not include a group represented by -X-C(=Y)-NH- include compounds represented by Formula U1.

U1

[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] The method for producing the inorganic particles containing (meth)acryloyl groups includes, for example, a method comprising a step of hydrolyzing alkoxysilane to obtain an alkoxysilane hydrolyzate, a step of mixing the alkoxysilane hydrolyzate with powdered silica particles or a solvent-dispersed sol of silica particles and heating and stirring the mixture, a method of hydrolyzing the alkoxysilane in the presence of particles, etc. In one embodiment, the production method (inorganic particles containing (meth)acryloyl groups) preferably includes a method of hydrolyzing the 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, 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, when producing the (meth)acryloyl group-containing inorganic particles, a dehydrating agent may be added to promote the reaction.

[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, tetrabutoxymethane and the like.

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

[0202] In one embodiment, the (meth)acryloyl group-containing inorganic particles contain a group represented by -X-C(=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 -X-C(=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 preferably include acrylic particles and styrene-acrylic particles, more preferably include cross-linked acrylic particles and cross-linked styrene-acrylic particles, and further preferably include cross-linked methyl methacrylate particles and cross-linked methyl methacrylate-styrene particles.

[0206] “A particles” refer to particles containing A resin in the raw material.

[0207] Examples of commercially available products (acrylic particles) include Eposter MA1004 and MA1006 (both manufactured by Nippon Shokubai Co., Ltd.), Tactic FH-S005 (manufactured by Nippon Excellan Industries Co., Ltd.), Kemisuno MX-80H3wT, MX-150, MX-180TA, MX-300, MX-500, MX-1000, MX-1500H, MX-2000, MX-3000 (manufactured by Soken Chemical Co., Ltd.), Techpolymer MBX-5, MBX-8, SSX-101, SSX-102, SSX-103, SSX-105, SSX-108, SSX-110, SSX-115HXE, SSX-120, SSX-127 (manufactured by Sekisui Chemicals Co., Ltd.), etc.

[0208] Examples of commercially available products (styrene-acrylic particles) include Eposter MA2003 (manufactured by Nippon Shokubai Co., Ltd.), Techpolymer MSX and SMX (manufactured by Sekisui Chemicals Co., Ltd.), and the like.

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

[0210] Examples of commercially available products (polyacrylonitrile particles) include Taffic ASF (manufactured by Nippon Excellan Industries, Ltd.).

[0211] Examples of commercially available products (melamine particles) include Ester SS, Ester S, Ester FS, Ester S6, Ester S12 (manufactured by Nippon Shokubai Co., Ltd.), and the like.

[0212] Examples of commercially available products (polyethylene particles) include Mipelon XM-220 and XM221U (manufactured by Mitsui Chemicals, Inc.), Flowbez LE-1080 (manufactured by Sumitomo Seika Chemicals, Inc.), and Chemipal 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)) The particle size (inorganic particles) includes, for example, 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, 5 nm, etc. In one embodiment, the particle size is preferably 5 nm to 100 nm. The reasons for preference include, for example, hardness and bendability.

[0216] The particle size (organic particles) includes, for example, 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, 0.5 μm, etc. In one embodiment, the particle size is preferably 0.5 μm to 10 μm. The preferred reason is, for example, improved anti-glare performance.

[0217] “Particle size” refers to a volume average particle size. “Volume average particle size” refers to a particle size at which the particle size distribution (volume basis) accumulated from the smaller particle size side is 50% in a volume-based particle size distribution measured by a dynamic light scattering method.

[0218] The volume-based particle size distribution can be measured by the following procedure. <Inorganic particles> (1) Preparation of assay solution A solution is prepared by adding a measurement sample (particles) to propylene glycol monomethyl ether (PGME: for example, manufactured by Nippon Emulsifier Co., Ltd.) so that the measurement sample concentration becomes 1% by mass. (2) Determination of volume-based particle size distribution 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 Determination limit: 1nm Measuring solvent: PGME Refractive index: 1.404 <Organic particles> (1) Determination of volume-based particle size distribution Measuring machine: "Microtrac MT3000II" (Microtrac BEL) Number of measurements: 2 Measuring temperature: room temperature Measurement time: 30 seconds Measuring upper limit: 1400μm Determination limit: 0.2μm Measuring solvent: PGME Refractive index: 1.404 The refractive index of the measured sample (particles) can be determined by referring to literature values ​​("A GUIDE FOR ENTERING MICROTRAC" RUN INFORMATION" (F3) DATA", produced by Leeds & Northrup Co., Ltd.) or the like.

[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, and 1.2. 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 was 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 irregular shapes.

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

[0224] The mass % content (particles / active energy ray-curable composition non-volatile component) includes, for example, 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 %, more preferably 0 mass % to 40 mass %.

[0225] The mass % content (inorganic particles / active energy ray-curable composition non-volatile component) includes, for example, 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 %, more preferably 0 mass % to 40 mass %.

[0226] The mass % content (organic particles / active energy ray-curable composition non-volatile component) includes, 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 %, more preferably 0 mass % to 20 mass %.

[0227] <Photopolymerization initiator> In one embodiment, the active energy ray-curable composition may optionally include a photopolymerization initiator. The photopolymerization initiator may be used alone or in combination of two or more.

[0228] Examples of the photopolymerization initiator include an α-hydroxydimethylacetophenone group-containing photopolymerization initiator, α-hydroxyphenylcycloalkyl ketone, α-aminophenylalkyl ketone, benzyl dimethyl ketal, unsubstituted or substituted phenylalkyl ketone, unsubstituted or substituted benzil, unsubstituted or substituted benzophenone, acylphosphine oxide, substituted thioxanthone, and oxime ester.

[0229] Examples of the α-hydroxydimethylacetophenone group-containing photopolymerization initiator include 2-hydroxy-2-methyl-1-phenylpropanone, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-methylpropanone, and 2-hydroxy-1-(4-(4-(2-hydroxy-2-methylpropanoyl)benzyl)phenyl)-2-methylpropane-1-one.

[0230] Examples of the α-hydroxyphenylcycloalkyl ketone include 1-hydroxycyclohexyl phenyl ketone and the like.

[0231] Examples of α-aminophenylalkyl ketone include 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropane-1-one and the like.

[0232] Examples of benzyl dimethyl ketal include 2,2-dimethoxy-1,2-diphenylethane-1-one.

[0233] Examples of the unsubstituted or substituted alkyl phenone 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′-morpholinobutylphenone, 2-methyl-4′-(methylthio)-2-morpholinopropiophenone, 2-isonitrosopropiophenone, and 2,2-dimethoxy-1,2-diphenylethane-1-one.

[0234] Examples of the unsubstituted or substituted benzil include benzil and anisil (p-anisil).

[0235] Examples of the unsubstituted or substituted benzophenone 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 and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide.

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

[0238] Examples of oxime esters include 1,2-octanedione, 1-[4-(phenylthio)-, 2-(o-benzoyloxime)] (1,2-oktandione, 1-[4-(fenilthio)-, 2-(o-benziloxime)]) (i.e., 2-((benzoyloxy)imino)-1-(4-(phenylthio)phenyl)octan-1-one); Ethyl ketone,1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-,1-(ortho Acetyl oxime)(エタノン,1-[9-エチル-6-(2-メチルベンゾイル)-9H-カルバゾール-3-イル]-, 1-(O-アセチルオキシム)) (i.e. 1-(((1-(9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl)ethylene)amino)oxy)ethane-1-one, etc.

[0239] When electron beam curing is performed, no photopolymerization initiator is required.

[0240] The mass % content (photopolymerization initiator / active energy ray-curable composition non-volatile component) includes, for example, 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 %, 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.

[0242] Examples of the polymerization inhibitor include hindered phenols.

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

[0244] Examples of hindered phenols include monohindered phenols.

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

[0246] Examples of the mono-hindered phenol include 2,6-di-tert-butyl-p-cresol and the like.

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

[0248] The mass % content (polymerization inhibitor / active energy ray-curable composition non-volatile component) includes, for example, 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 %, more preferably 0.01 mass % to 0.2 mass %.

[0249] <Organic solvents> In one embodiment, the active energy ray-curable composition may optionally contain an organic solvent. The organic solvent may be used alone or in combination of two or more.

[0250] Examples of the organic solvent include ketone solvents, aromatic solvents, alcohol solvents, glycol solvents, glycol ether solvents, ester solvents, petroleum solvents, alkyl halide solvents, and amide solvents.

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

[0252] Examples of the aromatic solvent include toluene and xylene.

[0253] Examples of the alcohol solvent include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, and tert-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 the glycol ether solvent 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-tert-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 petroleum-based solvents include Sepulchroic #100 (manufactured by Sequoia Co., Ltd.), Securum Co., Ltd. #150 (manufactured by Seiko Noon Co., Ltd.), and the like.

[0258] Examples of the halogenated alkyl solvent include chloroform and the like.

[0259] Examples of the amide solvent include dimethylformamide.

[0260] In one embodiment, the organic solvent preferably includes an alcohol solvent and a glycol ether solvent, more preferably includes isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, and propylene glycol monomethyl ether, further preferably includes a combination of isopropyl alcohol and propylene glycol monomethyl ether, a combination of n-butyl alcohol and propylene glycol monomethyl ether, and particularly preferably includes a combination of isopropyl alcohol and propylene glycol monomethyl ether. The preferred reason is, for example, improved leveling properties.

[0261] The mass % content (organic solvent / active energy ray-curable composition) includes, for example, 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 belong to any of the above.

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

[0264] In one embodiment, the content (additive / active energy ray-curable composition) is preferably less than 5 parts by mass, less than 1 part by mass, less than 0.1 part by mass, less than 0.01 part by mass, or 0 part by mass.

[0265] In one embodiment, the content by mass (additive / polymer), the content by mass (additive / poly(meth)acrylate without urethane bond), and the content by mass (additive / urethane poly(meth)acrylate) are preferably less than 5 parts by mass, less than 1 part by mass, less than 0.1 part by mass, less than 0.01 part by mass, 0 part by mass, etc.

[0266] The active energy ray-curable composition can be produced by dispersing and mixing the above-mentioned reagents.

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

[0268] Examples of the application (active energy ray-curable composition) include coating agents, hard coating agents, clear coating agents, clear hard coating agents, antiglare coating agents, antiglare 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. In addition, the components in the table are 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 material] The present disclosure relates to a cured product of the active energy ray-curable composition.

[0271] Examples of curing conditions include the following conditions.

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

[0273] The manufacturing method (laminate) includes, for example, the following steps. Active energy ray curable composition coating step: a step of coating the active energy ray curable composition on at least one side of the substrate Active energy ray curing step: a step of forming a cured product layer of the active energy ray curable composition by irradiating the substrate with active energy ray

[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 (substrate) is preferably 10 μm to 2000 μm.

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

[0277] (Coating process) Examples of the coating method include rod 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 active energy rays include ultraviolet rays and electron beams.

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

[0280] When a high pressure mercury lamp is used, the following conditions are preferably mentioned as curing conditions. Lamp output: 25W / cm~160W / cm UV illumination: 10mW / cm 2 ~800mW / cm 2 Accumulated light intensity: 25mJ / cm 2 ~2000mJ / cm 2 Conveying speed: 1m / min~50m / min

[0281] When an electron beam is used, the following conditions are preferably mentioned as curing conditions. Accelerating voltage: 10kV~300kV Conveying speed: 5m / min~50m / min [Example]

[0282] The present invention is specifically described below by examples and comparative examples. However, the above description and the following examples are not recorded for the purpose of limiting the present invention. The present invention is limited only by the scope of the claims. Unless otherwise specified, the numerical values ​​such as parts and % are based on mass.

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

[0284] Unless otherwise specified, other examples are carried out in the same manner as described above except for changes as shown in the following table.

[0285]

Table 1

[0286] Comparative Manufacturing Example 1-1 Into a four-necked flask equipped with a stirrer, a thermometer, a reflux cooler, and a nitrogen inlet, 125 parts of butyl acetate, 100 parts of glycidyl methacrylate (hereinafter referred to as GMA), and 1 part of azobisisobutyronitrile (hereinafter referred to as AIBN) were added, stirred, heated to 85° C. under a nitrogen stream, and then reacted for 10 hours. After the reaction was completed, it was cooled to 60° C., 50 parts of acrylic acid, 0.1 parts of triphenylphosphine, and 0.05 parts of p-methoxyphenol were added, the nitrogen inlet was replaced with an air bubbling device, and the reaction solution was stirred while bubbling air, and the temperature was raised to 110° C. and kept warm for 9 hours 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: 262 mgKOH / 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 Electric Co., Ltd. Heating rate: 10℃ / min

[0288] The weight average molecular weight, number average molecular weight and molecular weight distribution were measured under the following conditions. ·Measurement equipment: GPC (model: HLC-8420) manufactured by Tosoh Corporation Column: Product name "TSKgel SuperHZM-M" (manufactured by Tosoh Corporation) × 3 ·Eluent: Tetrahydrofuran Column temperature: 40°C Calibration curve: monodisperse polystyrene Detector: refractive index (RI) ·Polymer concentration: 1 mass% ·Measurement method: Measure after filtering.

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

[0290] Unless otherwise specified, other examples are carried out in the same manner as described above except for changes as shown in the following table.

[0291]

Table 2

[0292] Example 1: Active energy ray-curable composition The substances described in the following table were mixed as nonvolatile components, and then diluted with PGME to obtain an active energy ray-curable composition (nonvolatile content: 30%).

[0293] Unless otherwise specified, other examples are carried out in the same manner as described above except for changes as shown in the following table.

[0294]

Table 3

Table 4

[0295] (Laminate) The active energy ray-curable composition was applied to a substrate under the following conditions, and then the applied product was dried under the following conditions. Next, the dried product was cured under the following conditions to obtain a laminate. Coating conditions Substrate: TAC film, product name "FT TD80UL", manufactured by Fujifilm Co., Ltd. Coating method: Rod coater, model "No.13", manufactured by RD SPECIALTIES Film thickness: about 5μm Drying conditions 80℃ 1 minute (in circulating air dryer) Curing conditions Irradiation distance: 20cm Belt speed: 5m / min Cumulative irradiation: 200mJ / cm 2

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

[0297] (Occurrence of linear streaks) The surface of the coating film was visually observed for traces of unevenness caused by the bar coater. ○: No trace △: Only a tiny trace ×: There are clear traces

[0298] (Occurrence of defects) The defects generated on the coating film surface were visually observed. ○: The defect is not obvious △: Defects are partially evident. ×: All defects are obvious.

[0299] (Mandrel test) Standard: JIS K5600-5-1 (1999) Testing machine: Cylindrical mandrel bending tester Measurement value: Minimum diameter without observed cracking or peeling (mm)

[0300] Unless otherwise specified, the evaluation examples were performed in the same manner as in the above-mentioned examples except that the evaluation examples were changed as shown in the following table.

[0301]

Table 5

[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] (Haze) Standard: JIS K 7136 (2000) Measuring instrument: Haze meter, product name "HZ-V3", manufactured by Suga Testing Instrument Co., Ltd.

[0304] (Glossiness) Standard: JIS Z 8741(1997) Measuring machine: 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 poly(meth)acrylate not containing a urethane bond, and a urethane poly(meth)acrylate. The glass transition temperature of the polymer is 50° C. or higher. 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 . A laminate comprising the cured product according to claim 3.

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