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 containing a di (ethylenically unsaturated) compound not containing a urethane bond and a poly (ethylenically unsaturated) compound containing a urethane bond, the di (ethylenically unsaturated) compound not containing a urethane bond having a molecular weight of 260 or less.

Description

Technical Field

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

[0002] In various fields such as coating agents, active energy ray curable compositions have been used (for example, Patent Document 1). [Prior Art Documents] [Patent Documents]

[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 capable of producing a cured product having good adhesiveness. [Technical Means for Solving the Technical Problem]

[0005] According to the present disclosure, the following items are provided. (Item 1) An active energy ray curable composition comprising a bis(ethylenically unsaturated) compound having no urethane bond and a poly(ethylenically unsaturated) compound having a urethane bond, wherein the bis(ethylenically unsaturated) compound having no urethane bond has a molecular weight of 260 or less. (Item 2) The active energy ray curable composition according to the above 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 according to the above item.

[0006] In the present disclosure, in addition to the combinations explicitly shown, the one or more features may be further combined and provided. [Advantageous Effects]

[0007] The cured product of the present invention exhibits good adhesiveness. Detailed Description of the Invention

[0008] Throughout the present disclosure, the ranges of physical property values, contents, and other numerical values can be appropriately set (for example, selected from the values described in the following items). Specifically, regarding the numerical value α, when A3, A2, A1 (assuming A3 > A2 > A1) are given, the range of the numerical value α can 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 A3 or less, greater than A1 and A2 or less, greater than A2 and A3 or less, etc.

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

[0010] The “αβ amount (A / B)” means the β amount (α) of A relative to 100α of B. α is, for example, mass%, mol%, parts by mass, etc. The β amount is, for example, content, usage amount, etc. The “mass% content (A / B)” means the content (mass%) of A relative to 100 mass% of B.

[0011] The “γ ratio (A / B)” means the γ ratio calculated by the formula “A ÷ B”. The γ ratio is, for example, mass ratio, molar ratio, etc.

[0012] The “non-volatile component” means the total mass of components other than organic solvents and water.

[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] “(Meth)allyl” means “allyl and / or methallyl”.

[0015] “C···” means “having ··· carbon atoms”. For example, “C1-6 alkyl” means “alkyl having 1 to 6 carbon atoms”. “C6 alkyl” means “alkyl having 6 carbon atoms”.

[0016] Examples of the alkyl group include linear alkyl groups, branched alkyl groups, cycloalkyl groups, etc.

[0017] Examples of the linear alkyl group include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, etc.

[0018] Examples of the branched alkyl group include isopropyl, 2-ethylhexyl, diethylpentyl, trimethylbutyl, trimethylpentyl, trimethylhexyl, etc.

[0019] Examples of cycloalkyl groups include monocyclic cycloalkyl groups, bridged cycloalkyl groups, fused cycloalkyl groups, etc. In addition, a group in which at least one hydrogen atom of the cycloalkyl group is substituted by an alkyl group is also regarded as a cycloalkyl group.

[0020] "Monocyclic" refers to a cyclic structure formed by covalent bonds of carbon without an internal bridging structure. "Fused ring" refers to a cyclic structure in which two or more monocyclic rings share two atoms (i.e., only one side of each ring is shared (fused) with each other). "Bridged ring" refers to a cyclic structure in which two or more monocyclic rings share three or more atoms.

[0021] Examples of monocyclic cycloalkyl groups include cyclopentyl, cyclohexyl, cycloheptyl, cyclodecyl, 3,5,5-trimethylcyclohexyl, etc.

[0022] Examples of bridged cycloalkyl groups include tricyclodecyl, adamantyl, norbornyl, etc.

[0023] In addition, the alkyl group also includes a group combining a straight-chain alkyl group, a branched-chain alkyl group, and a cycloalkyl group. Examples of the combined group include cycloalkylalkyl, etc.

[0024] Cycloalkylalkyl is represented by the following formula. R calkyl -R alkyl - (In the formula, R calkyl represents a cycloalkyl group. R alkyl represents an alkyl group.)

[0025] Examples of alkylene groups include straight-chain alkylene groups, branched-chain alkylene groups, cycloalkylene groups, etc.

[0026] Examples of straight-chain alkylene groups include methylene, ethylene, n-propylene, n-butylene, n-pentylene, n-hexylene, n-heptylene, n-octylene, n-nonylene, n-decylene, etc.

[0027] Examples of branched-chain alkylene groups include diethylpentylene, trimethylbutylene, trimethylpentylene, trimethylhexylene, etc.

[0028] Examples of cycloalkylene groups include monocyclic cycloalkylene groups, bridged cycloalkylene groups, fused cycloalkylene groups, etc. In addition, one or more hydrogen atoms of the cycloalkylene group may be substituted by a straight-chain alkyl group or a branched-chain alkyl group.

[0029] Examples of monocyclic cycloalkylene groups include cyclopentylene, cyclohexylene, cycloheptylene, cyclodecylene, 3,5,5-trimethylcyclohexylene, etc.

[0030] Examples of bridged cycloalkylene groups include tricyclodecylene, adamantylene, norbornylene, etc.

[0031] Examples of fused cycloalkylene groups include bicyclodecylene, etc.

[0032] In addition, the alkylene group also includes a group combining a linear alkylene group, a branched alkylene group, and a cycloalkylene group. Examples of the combined group include a cycloalkylalkylene group, an alkylcycloalkylalkylene group, and the like.

[0033] The cycloalkylalkylene group is represented by the following formula. -R calkylene -R alkylene - (In the formula, R calkylene represents a cycloalkylene group. R alkylene represents an alkylene group.)

[0034] The alkylcycloalkylalkylene group is represented by the following formula. -R alkylene -R calkylene -R alkylene - (In the formula, R calkylene represents a cycloalkylene group. R alkylene represents an alkylene group.)

[0035] 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, a carbonylaryl group, and the like.

[0036] Examples of the aryl group include a monocyclic aryl group, a polycyclic aryl group, and the like.

[0037] Examples of the monocyclic aryl group include a phenyl group, a tolyl group, a mesityl group (2,4,6-trimethylphenyl), and the like.

[0038] Examples of the polycyclic aryl group include a naphthyl group and the like.

[0039] Examples of the arylene group include a monocyclic arylene group, a polycyclic arylene group, and the like.

[0040] Examples of the monocyclic arylene group include a phenylene group, a tolylene group, and the like.

[0041] Examples of the polycyclic arylene group include a naphthylene group and the like.

[0042] [Actinic energy ray curable composition: Composition] The present disclosure relates to an actinic energy ray curable composition, the actinic energy ray curable composition comprising: a bis(ethylenically unsaturated) compound having no urethane bond and a poly(ethylenically unsaturated) compound having a urethane bond, wherein the molecular weight of the bis(ethylenically unsaturated) compound having no urethane bond is 260 or less.

[0043] <Bis(ethylenically unsaturated) compound having no urethane bond> The bis(ethylenically unsaturated) compounds without urethane bonds can be used alone or in combination of two or more.

[0044] The "bis(ethylenically unsaturated) compound without urethane bonds" refers to a "compound without urethane bonds having 2 ethylenically unsaturated bonds".

[0045] Examples of the group containing an ethylenically unsaturated bond include (meth)acryloyl group, (meth)allyl group, vinyl group, etc.

[0046] Examples of the bis(ethylenically unsaturated) compound without urethane bonds include (poly)alkylene glycol di(meth)acrylate, (meth)acrylate containing a vinyl ether group, etc.

[0047] In one embodiment, the (poly)alkylene glycol di(meth)acrylate is represented by the following structural formula. [Chemical formula AD] (In the formula, r represents 1 or 2. R ad1 , R ad3 each independently represents an acryloyl group or a methacryloyl group. R ad2 represents an alkylene group.) In one embodiment, when r = 1, R ad1 = R ad3 = acryloyl group, R ad2 represents a C1-C8 alkylene group. when r = 1, R ad1 = R ad3 = methacryloyl group, R ad2 represents a C1-C6 alkylene group. when r = 2, R ad1 = R ad3 = acryloyl group, R ad2 represents a C1-C3 alkylene group. when r = 2, R ad1 = R ad3 = methacryloyl group, R ad2 represents a C1-C2 alkylene group.

[0048] Examples of the (poly)alkylene glycol di(meth)acrylate include alkylene glycol diacrylate, alkylene glycol dimethacrylate, polyalkylene glycol diacrylate, polyalkylene glycol dimethacrylate, etc. Examples of the alkylene glycol diacrylate include ethylene glycol diacrylate (molecular weight: 170), propylene glycol diacrylate (molecular weight: 184), butylene glycol diacrylate (molecular weight: 198), pentylene glycol diacrylate (molecular weight: 212), hexylene glycol diacrylate (molecular weight: 226), heptylene glycol diacrylate (molecular weight: 240), octylene glycol diacrylate (molecular weight: 254), nonylene glycol diacrylate (molecular weight: 268), neopentyl glycol diacrylate (molecular weight: 212), etc.

[0049] Examples of the alkylene glycol dimethacrylate include ethylene glycol dimethacrylate (molecular weight: 198), propylene glycol dimethacrylate (molecular weight: 212), butylene glycol dimethacrylate (molecular weight: 226), pentylene glycol dimethacrylate (molecular weight: 240), hexylene glycol dimethacrylate (molecular weight: 254), neopentyl glycol dimethacrylate (molecular weight: 24 0), etc.

[0050] Examples of the polyalkylene glycol diacrylate include diethylene glycol diacrylate (molecular weight: 214), dipropylene glycol diacrylate (molecular weight: 242), triethylene glycol diacrylate (molecular weight: 258), etc.

[0051] Examples of the polyalkylene glycol dimethacrylate include diethylene glycol dimethacrylate (molecular weight: 242), etc.

[0052] Examples of the (meth)acrylate containing a vinyl ether group include 2-(2-vinyloxyethoxy)ethyl acrylate (molecular weight: 186), 2-(2-vinyloxyethoxy)ethyl methacrylate (molecular weight: 200), etc.

[0053] Molecular weights (of the bis(ethylenically unsaturated) compounds without a urethane bond) include, for example, 260, 258, 255, 254, 250, 245, 242, 240, 235, 230, 226, 225, 220, 215, 214, 212, 210, 205, 200, 198, 195, 190, 186, 185, 184, 180, 175, 170, etc. In one embodiment, the molecular weight is preferably 260 or less, more preferably 170 to 260.

[0054] The mass % content (a di(ethylenically unsaturated) compound free of urethane bonds / non-volatile components of the active energy ray curable composition) includes, for example, 50 mass%, 45 mass%, 40 mass%, 35 mass%, 30 mass%, 25 mass%, 20 mass%, 15 mass%, 10 mass%, 5 mass%, etc. In one embodiment, the content is preferably 5 mass% to 50 mass%, and more preferably 10 mass% to 30 mass%.

[0055] <Poly(ethylenically unsaturated) compound containing a urethane bond> The poly(ethylenically unsaturated) compound containing a urethane bond can be used alone or in combination of two or more.

[0056] The "poly(ethylenically unsaturated) compound containing a urethane bond" means a "compound containing a urethane bond and having two or more ethylenically unsaturated bonds".

[0057] Examples of the poly(ethylenically unsaturated) compound containing a urethane bond include reaction products of a compound group including a hydroxy group-containing poly(meth)acrylate and a polyisocyanate, etc.

[0058] <Hydroxy group-containing poly(meth)acrylate> Examples of the hydroxy group-containing poly(meth)acrylate include hydroxy group-containing (poly)pentaerythritol poly(meth)acrylate, hydroxy group-containing (poly)trimethylolpropane poly(meth)acrylate, hydroxy group-containing (poly)glycerol poly(meth)acrylate, etc.

[0059] The polyisocyanate can be used alone or in combination of two or more.

[0060] <Polyisocyanate> The "polyisocyanate" means a compound having two or more isocyanate groups (-N=C=O).

[0061] Examples of the polyisocyanate include linear aliphatic polyisocyanates, branched aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic polyisocyanates, and their biuret forms, isocyanurate forms, urethane forms, adduct forms, etc.

[0062] 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, decamethylene diisocyanate, etc.

[0063] Examples of the branched aliphatic polyisocyanate include diethylvalylene diisocyanate, trimethylbutylene diisocyanate, trimethylpentylene diisocyanate, trimethylhexamethylene diisocyanate, etc.

[0064] Examples of alicyclic polyisocyanates include monocyclic alicyclic polyisocyanates, bridged-ring alicyclic polyisocyanates, fused-ring alicyclic polyisocyanates, etc.

[0065] Examples of monocyclic alicyclic polyisocyanates include hydrogenated xylylene diisocyanate, isophorone diisocyanate, cyclopentylene diisocyanate, cyclohexylene diisocyanate, cycloheptylene diisocyanate, cyclodecylene diisocyanate, 3,5,5-trimethylcyclohexylene diisocyanate, dicyclohexylmethane diisocyanate, etc.

[0066] Examples of bridged-ring alicyclic polyisocyanates include tricyclodecylene diisocyanate, adamantane diisocyanate, norbornene diisocyanate, etc.

[0067] Examples of fused-ring alicyclic polyisocyanates include bicyclodecylene diisocyanate, etc.

[0068] Examples of aromatic polyisocyanates include monocyclic aromatic polyisocyanates, fused-ring aromatic polyisocyanates, etc.

[0069] Examples of monocyclic aromatic polyisocyanates 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, tolylene diisocyanate, xylylene diisocyanate, m-tetramethylxylylene diisocyanate, etc.

[0070] Examples of fused-ring aromatic polyisocyanates include 1,5-naphthalene diisocyanate, etc.

[0071] In one embodiment, the poly(ethylenically unsaturated) compound containing a urethane bond is preferably a poly(ethylenically unsaturated) compound containing a urethane bond having (poly)pentaerythritol poly(meth)acrylate in the structural unit, more preferably a reaction product of (poly)pentaerythritol poly(meth)acrylate with any one of allophanate form, biuret form, and urethane form of a linear aliphatic polyisocyanate, and still more preferably a reaction product of (poly)pentaerythritol poly(meth)acrylate with any one of allophanate form and biuret form of hexamethylene diisocyanate.

[0072] Weight-average molecular weight: Mw (poly(ethylenically unsaturated) compound containing a carbamate bond) is, for example, 150,000, 120,000, 100,000, 80,000, 60,000, 50,000, 40,000, 30,000, 2000 0, 15,000, 10,000, 9000, 8000, 7000, 6000, 5000, 4000, 3000, 2000, 1500, etc. In one embodiment, the weight-average molecular weight is preferably selected from 1500 to 150,000, more preferably from 2000 to 20,000. The reasons for the preference are, for example, improvement in leveling property, etc.

[0073] Number-average molecular weight: Mn (poly(ethylenically unsaturated) compound containing a carbamate bond) is, for example, 30,000, 2000 0, 15,000, 10,000, 9000, 8000, 7000, 6000, 5000, 4000, 3000, 2000, 1200, 1000, etc. In one embodiment, the number-average molecular weight is preferably selected from 1000 to 30,000, more preferably from 1000 to 15,000, and further preferably from 1200 to 8000. The reasons for the preference are, for example, improvement in leveling property, etc.

[0074] Molecular weight distribution: Mw / Mn (poly(ethylenically unsaturated) compound containing a carbamate bond) is, for example, 8, 7, 6, 5, 4.5, 4, 3.5, 3, 2.5, 2.3, 2.1, 1.5, 1.4, 1.3, 1.2, 1.1, 1.0, etc. In one embodiment, the molecular weight distribution is preferably selected from 1.0 to 5, more preferably 4 or less, and further preferably 3 or less. The reasons for the preference are, for example, improvement in leveling property, etc.

[0075] The measurement conditions for the weight-average molecular weight (poly(ethylenically unsaturated) compound containing a carbamate bond) and the number-average molecular weight (poly(ethylenically unsaturated) compound containing a carbamate bond) are, for example, the conditions described later, etc.

[0076] Double bond equivalent (poly(ethylenically unsaturated) compound containing a carbamate bond) is, for example, 300 g / eq, 290 g / eq, 275 g / eq, 250 g / eq, 225 g / eq, 200 g / eq, 190 g / eq, 175 g / eq, 150 g / eq, 125 g / eq, 120 g / eq, etc. In one embodiment, the double bond equivalent is preferably selected from 120 g / eq to 300 g / eq.

[0077] The mass% content (poly(ethylenically unsaturated) compound containing a urethane bond / non-volatile component of the active energy ray-curable composition) includes, for example, 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%, etc. In one embodiment, the content is preferably selected from 5 mass% to 80 mass%.

[0078] <Tris or more (ethylenically unsaturated) compounds without a urethane bond> In one embodiment, the active energy ray-curable composition may optionally contain tris or more (ethylenically unsaturated) compounds without a urethane bond. The tris or more (ethylenically unsaturated) compounds without a urethane bond can be used alone or in combination of two or more.

[0079] "Tris or more (ethylenically unsaturated) compounds without a urethane bond" means "compounds without a urethane bond having 3 or more ethylenically unsaturated bonds".

[0080] Examples of the tris or more (ethylenically unsaturated) compounds without a urethane bond include poly(meth)acrylates without a urethane bond, etc.

[0081] "Poly(meth)acrylate" means a compound having two or more (meth)acryloyl groups.

[0082] Examples of the tris or more (ethylenically unsaturated) compounds without 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, poly(alkylene oxide-modified or epoxy-modified) (meth)acrylate containing an isocyanurate structure, (poly)alkylene di(poly(alkylene oxide-modified or epoxy-modified) (meth)acrylate, bisphenol A di(poly(alkylene oxide-modified or epoxy-modified) (meth)acrylate, etc.

[0083] "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.

[0084] The number of (meth)acryloyl groups (tris or more (ethylenically unsaturated) compounds without a urethane bond) includes, for example, 20, 19, 18, 17, 16, 15, 14, 13, 12, 11, 10, 9, 8, 7, 6, 5, 4, 3, etc. In one embodiment, the number is preferably selected from 3 to 20.

[0085] <(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 the formula (A’). [Chemical formula A1] [In the formula, n represents an integer from 0 to 2. R b1’ ~R b6’ each independently represents a hydrogen atom, [Chemical formula A2] R b4’ and R b5’ may be different groups for each structural unit. In the formula (A ’ ), there are two or more [Chemical formula A3] q represents an integer from 0 to 16. R 1’ ~R 3’ each independently represents a hydrogen atom or an alkyl group. R 1’ may be different groups for each unit.]

[0086] In addition, "may be different groups for each structural unit" means that in the formula (A’), for example, when n is 2, [Chemical formula A4] R b4A and R b4B may be different groups, and R b5A and R b5B may be different groups.

[0087] Examples of pentaerythritol poly(meth)acrylate include pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, etc.

[0088] Examples of 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), pentaerythritol tetra(propylene oxide-modified (meth)acrylate), etc.

[0089] Pentaerythritol polyepoxy-modified (meth)acrylates include, for example, pentaerythritol diepoxy (meth)acrylate, pentaerythritol triepoxy (meth)acrylate, pentaerythritol tetraepoxy (meth)acrylate, etc.

[0090] Polypentaerythritol poly(meth)acrylates include, for example, 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, tripentaerythritol octa(meth)acrylate, etc.

[0091] Polypentaerythritol polyalkylene oxide-modified (meth)acrylates include, for example, 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), 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 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), tripentaerythritol octa(propylene oxide-modified (meth)acrylate), etc.

[0092] Examples of poly-pentaerythritol poly-epoxy-modified (meth)acrylates 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, tripentaerythritol octaepoxy (meth)acrylate, etc.

[0093] <(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’), etc. [Chemical formula B1] [In the formula, m represents an integer from 0 to 2. R b7’ ~R b10’ each independently represents a hydrogen atom, [Chemical formula B2] R b9’ for each structural unit, it can be a different group. Formula (B ’ ) contains two or more [Chemical formula B3] q represents an integer from 0 to 16. R 1’ ~R 3’ each independently represents a hydrogen atom or an alkyl group. R 1’ for each unit, it can be a different group. ]

[0094] Examples of trimethylolpropane poly(meth)acrylate include trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, etc.

[0095] Examples of trimethylolpropane polyalkylene oxide-modified (meth)acrylate include trimethylolpropane bis(ethylene oxide-modified (meth)acrylate), trimethylolpropane tris(ethylene oxide-modified (meth)acrylate), trimethylolpropane bis(propylene oxide-modified (meth)acrylate), trimethylolpropane tris(propylene oxide-modified (meth)acrylate), etc.

[0096] Trimethylolpropane polyepoxy modified (meth)acrylate includes, for example, trimethylolpropane diepoxy (meth)acrylate, trimethylolpropane triepoxy (meth)acrylate, etc.

[0097] Polytrihydroxymethylpropane poly(meth)acrylate includes, for example, bis-trimethylolpropane di(meth)acrylate, bis-trimethylolpropane tri(meth)acrylate, bis-trimethylolpropane tetra(meth)acrylate, etc.

[0098] Polytrihydroxymethylpropane polyepoxyalkane modified (meth)acrylate includes, for example, bis-trimethylolpropane di(ethylene oxide modified (meth)acrylate), bis-trimethylolpropane tri(ethylene oxide modified (meth)acrylate), bis-trimethylolpropane tetra(ethylene oxide modified (meth)acrylate), bis-trimethylolpropane di(propylene oxide modified (meth)acrylate), bis-trimethylolpropane tri(propylene oxide modified (meth)acrylate), bis-trimethylolpropane tetra(propylene oxide modified (meth)acrylate), etc.

[0099] Polytrihydroxymethylpropane polyepoxy modified (meth)acrylate includes, for example, bis-trimethylolpropane diepoxy (meth)acrylate, bis-trimethylolpropane triepoxy (meth)acrylate, bis-trimethylolpropane tetraepoxy (meth)acrylate, etc.

[0100] <(Poly)glycerol poly(epoxyalkane modified or epoxy modified)(meth)acrylate> (Poly)glycerol poly(epoxyalkane modified or epoxy modified)(meth)acrylate is a compound represented by formula (C’), etc. [Chemical formula C1] [In the formula, p represents an integer from 0 to 7. R b11’ ~R b14’ Each independently represents a hydrogen atom, [Chemical formula C2] R b13’ For each structural unit, it can be a different group. Formula (C ’ ) contains two or more [Chemical formula C3] q represents an integer from 0 to 16. R 1’ ~R 3’ Each independently represents a hydrogen atom or an alkyl group. R 1’ For each unit, it can be a different group.]

[0101] Examples of glycerol poly(meth)acrylates include glycerol di(meth)acrylate, glycerol tri(meth)acrylate, etc.

[0102] Examples of glycerol poly(alkylene oxide) modified (meth)acrylates include glycerol di(ethylene oxide modified (meth)acrylate), glycerol tri(ethylene oxide modified (meth)acrylate), glycerol di(propylene oxide modified (meth)acrylate), glycerol tri(propylene oxide modified (meth)acrylate), etc.

[0103] Examples of glycerol poly(epoxy) modified (meth)acrylates include glycerol diepoxy(meth)acrylate, glycerol triepoxy(meth)acrylate, etc.

[0104] 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, triglycerol penta(meth)acrylate, etc.

[0105] Examples of polyglycerol poly(alkylene 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), 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), etc.

[0106] Examples of polyglycerol poly(epoxy) 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, triglycerol pentaepoxy(meth)acrylate, etc.

[0107] <Poly(alkylene oxide modified or epoxy modified) (meth)acrylate containing isocyanurate structure> The poly(alkylene oxide modified or epoxy modified) (meth)acrylate containing isocyanurate structure is a compound represented by the formula (D’), etc. [Chemical Formula D1] [In the formula, R b15’ ~R b17’ each independently represents a hydrogen atom, [Chemical Formula D2] Formula (D ’ ) contains two or more [Chemical Formula D3] q represents an integer from 0 to 16. R 1’ ~R 3’ each independently represents a hydrogen atom or an alkyl group. R 1’ For each unit, it can be a different group.]

[0108] Examples of poly(meth)acrylates containing an isocyanurate structure include di(meth)acryloyl isocyanurate, tri(meth)acryloyl isocyanurate, etc.

[0109] Examples of polyalkylene oxide-modified (meth)acrylates containing an isocyanurate structure include di(ethylene oxide-modified (meth)acryloyl) isocyanurate, tri(ethylene oxide-modified (meth)acryloyl) isocyanurate, etc.

[0110] Examples of polyepoxy-modified (meth)acrylates containing an isocyanurate structure include di-epoxy-modified (meth)acryloyl isocyanurate, tri-epoxy-modified (meth)acryloyl isocyanurate, etc.

[0111] Examples of the hydroxyl value (a compound having three or more (ethylenically unsaturated) groups excluding urethane bonds) include 300 mgKOH / g, 275 mgKOH / g, 250 mgKOH / g, 225 mgKOH / g, 200 mgKOH / g, 175 mgKOH / g, 150 mgKOH / g, 125 mgKOH / g, 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 selected from 0 mgKOH / g to 300 mgKOH / g. Examples of the reason for the preference include improvement of antiglare property, etc.

[0112] Mass % content (compound with three or more (ethylenically unsaturated) groups not containing a urethane bond / non-volatile components of the active energy ray curable composition) 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%, 5 mass%, 0 mass%, etc. In one embodiment, the content is preferably selected from 0 mass% to 90 mass%, and more preferably from 0 mass% to 70 mass%.

[0113] <Particles> In one embodiment, the active energy ray curable composition may optionally contain particles. The particles can be used alone or in combination of two or more.

[0114] Examples of the particles include inorganic particles, organic particles, etc.

[0115] (Inorganic Particles) Examples of the inorganic particles include metal oxide particles, silica particles, etc.

[0116] Examples of the metal oxide particles include titanium oxide particles, zirconium oxide particles, niobium oxide particles, barium titanate particles, zinc oxide particles, etc.

[0117] In one embodiment, the particle state is preferably powder or solvent-dispersed sol.

[0118] When the particle form is a solvent-dispersed sol, the dispersion solvent is preferably an organic solvent.

[0119] The organic solvents can be used alone or in combination of two or more. Examples of the organic solvents include the organic solvents described below.

[0120] Inorganic particles containing a (meth)acryloyl group In one embodiment, the inorganic particles are preferably inorganic particles containing a (meth)acryloyl group.

[0121] The inorganic particles containing a (meth)acryloyl group are reaction products of inorganic particles and a compound containing a (meth)acryloyl group.

[0122] (Compound Containing a (Meth)acryloyl Group) The compound containing a (meth)acryloyl group can be used alone or in combination of two or more.

[0123] In one embodiment, the compound containing a (meth)acryloyl group contains a group represented by -X-C(=Y)-NH-. (In the formula, X represents NH, O or S. Y represents O or S.)

[0124] -X-C(=Y)-NH-, 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 can be used alone or in combination of two or more. In one embodiment, the group is preferably selected from -O-C(=O)-NH-, -O-C(=S)-NH-, -S-C(=O)-NH-. The reasons for preference include, for example, improved thermal stability, etc.

[0125] It is considered that the above group [-X-C(=Y)-NH-] generates appropriate cohesive force through hydrogen bonds between molecules, and imparts excellent mechanical strength, adhesion to the substrate, heat resistance and other properties when forming a cured product. In addition, the above is only one statement, and the present invention is not intended to be bound by the above statement.

[0126] The (meth)acryloyl group-containing compound is preferably selected from a compound containing a silanol group and a compound that generates a silanol group.

[0127] Examples of the compound that generates a silanol group 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 compound that generates a silanol group is preferably selected from compounds containing an alkoxy group or an aryloxy group.

[0128] The silanol group or the silanol group generation site of the compound that generates a silanol group is a structural unit bonded to the particles through a condensation reaction or a condensation reaction occurring after hydrolysis.

[0129] In one embodiment, the (meth)acryloyl group-containing compound is preferably selected from the compounds represented by the following formula S.

Chemical formula S1

[0130] In formula S, (R s1 O) s’ R s2 3－s’Si - Examples include trimethoxysilyl, triethoxysilyl, triphenoxysilyl, methyldimethoxysilyl, dimethylmethoxysilyl, etc. In one embodiment, (R s1 O) s’ R s2 3－s’ Si - Preferably, trimethoxysilyl and triethoxysilyl are selected.

[0131] In formula S, R s4 Examples include alkylene, arylene, etc. R s4 may optionally contain elements other than carbon atoms and hydrogen atoms. R s4 may optionally contain a polyether bond, a polyester bond, a polyamide bond, a polycarbonate bond, -X-C(=Y)-NH-. (In the formula, X represents NH, O, or S. Y represents O or S.)

[0132] The molecular weight of the formula (R s4 ) is preferably 14 to 10,000, more preferably 76 to 500.

[0133] In formula S, R s5 Examples include alkylene, arylene, etc. R s5 may optionally contain elements other than carbon atoms and hydrogen atoms. R s5 may optionally contain a polyether bond, a polyester bond, a polyamide bond, a polycarbonate bond, -X-C(=Y)-NH-. (In the formula, X represents NH, O, or S. Y represents O or S.)

[0134] R s5 Examples include the following groups, etc.

Chemical formula S2

[0135] In formula S, s” is preferably 1 to 20, more preferably 1 to 10, and further preferably 1 to 5.

[0136] Examples of the method for synthesizing the (meth)acryloyl group-containing compound represented by formula S include the method described in Japanese Patent Laid-Open No. 9-100111, etc. Examples of the synthesis method include the following methods, etc. (A) Method: Addition reaction of mercaptoalkoxysilane with polyisocyanate and (meth)acrylate containing an 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 (C) method: The addition reaction of a compound having a (meth)acryloyl group and an isocyanate group with a mercaptoalkoxysilane or an aminosilane

[0137] In one embodiment, the synthesis method of the (meth)acryloyl group-containing compound represented by formula S preferably selects the above-mentioned (A) method. Examples of the (A) method include the following methods. (A1) method is a method including the following steps: a step of first reacting a mercaptoalkoxysilane with a polyisocyanate to form an intermediate containing an alkoxysilyl group, a [–S–C(=O)NH–] group, and an isocyanate group; a step of reacting the intermediate with a hydroxy group-containing (poly)(meth)acrylate to form a [–O–C(=O)NH–] bond. (A2) method is a method including the following steps: a step of first reacting a polyisocyanate with a hydroxy group-containing (poly)(meth)acrylate to form an intermediate containing a (meth)acryloyl group, a [–O–C(=O)NH–] group, and an isocyanate group; a step of reacting a mercaptoalkoxysilane with the intermediate to form a [–S–C(=O)–NH–] bond In one embodiment, from the viewpoint that the polymerizable unsaturated group is not reduced by the Michael addition reaction, the (A1) method is preferred.

[0138] The mercaptoalkoxysilane can be used alone or in combination of two or more.

[0139] Examples of the mercaptoalkoxysilane include mercaptopropyltrimethoxysilane, mercaptopropyltriethoxysilane, mercaptopropylmethyldiethoxysilane, mercaptopropylmethyldimethoxysilane, mercaptopropylmethoxydimethylsilane, mercaptopropyltriphenoxysilane, mercaptopropyltributoxysilane, etc.

[0140] In one embodiment, the mercaptoalkoxysilane preferably selects mercaptopropyltrimethoxysilane and mercaptopropyltriethoxysilane.

[0141] The polyisocyanate can be used alone or in combination of two or more. Examples of the polyisocyanate include the above-mentioned compounds.

[0142] The hydroxy group-containing (poly)(meth)acrylate can be used alone or in combination of two or more.

[0143] Examples of the hydroxy group-containing (poly)(meth)acrylate include hydroxy group-containing (meth)acrylate, hydroxy group-containing poly(meth)acrylate, etc.

[0144] Hydroxyl-containing (meth)acrylates include, for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, 1,4-cyclohexanedimethanol mono(meth)acrylate, etc.

[0145] Hydroxyl-containing poly(meth)acrylates include, for example, the compounds described below, etc.

[0146] In one embodiment, preferred hydroxyl-containing poly(meth)acrylates include trimethylolpropane di(meth)acrylate, trimethylolethane di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate.

[0147] In one embodiment, preferred hydroxyl-containing (poly)(meth)acrylates include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, pentaerythritol tri(meth)acrylate.

[0148] 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.)

[0149] Examples of the (meth)acryloyl group-containing compound that does not contain a group represented by -X-C(=Y)-NH- include the compounds represented by the following formula, etc.

Chemical formula S3

[0150] Examples of the compound represented by Formula U1 include tris(meth)acryloyloxyethyl monomethoxysilane, bis(meth)acryloyloxyethyl dimethoxysilane, (meth)acryloyloxyethyl trimethoxysilane, tris(meth)acryloyloxypropyl monomethoxysilane, bis(meth)acryloyloxypropyl dimethoxysilane, (meth)acryloyloxypropyl trimethoxysilane, tris(meth)acryloyloxypropyl monoethoxysilane, bis(meth)acryloyloxypropyl diethoxysilane, (meth)acryloyloxypropyl triethoxysilane, tris(meth)acryloyloxypropyl monophenoxysilane, bis(meth)acryloyloxypropyl diphenoxysilane, (meth)acryloyloxypropyl triphenoxysilane, and the like.

[0151] Examples of the method for producing (meth)acryloyl group-containing inorganic particles include a method including a step of hydrolyzing an alkoxysilane to obtain an alkoxysilane hydrolysis product, and a step of mixing the alkoxysilane hydrolysis product with powder silica particles or a solvent-dispersed sol of silica particles and performing heating and stirring operations; a method of hydrolyzing an alkoxysilane in the presence of particles, and the like. In one embodiment, the production method (for (meth)acryloyl group-containing inorganic particles) preferably employs a method of hydrolyzing an alkoxysilane in the presence of particles.

[0152] The reaction temperature (for producing (meth)acryloyl group-containing inorganic particles) is preferably 0°C to 150°C, more preferably 20°C to 100°C.

[0153] The reaction time (for producing (meth)acryloyl group-containing inorganic particles) is preferably 5 minutes to 24 hours.

[0154] In one embodiment, when producing (meth)acryloyl group-containing particles, a dehydrating agent may be added to promote the reaction.

[0155] Examples of the dehydrating agent include inorganic dehydrating agents, organic dehydrating agents, and the like.

[0156] Examples of the inorganic dehydrating agent include zeolite, anhydrous silica, anhydrous alumina, and the like.

[0157] Examples of the organic dehydrating agent include methyl orthoformate, ethyl orthoformate, tetraethoxymethane, tetrabutoxymethane, and the like.

[0158] In one embodiment, the dehydrating agent preferably employs an organic dehydrating agent, more preferably methyl orthoformate and ethyl orthoformate.

[0159] 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.)

[0160] In one embodiment, the (meth)acryloyl group-containing inorganic particles do not contain a group represented by -X-C(=Y)-NH- (wherein X represents NH, O or S; and Y represents O or S).

[0161] (organic particles) Examples of the organic particles include acrylic particles, styrene-acrylic particles, polystyrene particles, polyacrylonitrile particles, melamine particles, polyethylene particles, benzoguanamine particles, etc.

[0162] In one embodiment, the organic particles are preferably selected from acrylic particles and styrene-acrylic particles, more preferably crosslinked acrylic particles and crosslinked styrene-acrylic particles, and still more preferably crosslinked methyl methacrylate particles and crosslinked methyl methacrylate-styrene particles.

[0163] "A particles" means particles containing A resin in the raw materials.

[0164] Examples of commercially available products (acrylic particles) include Eposter MA1004, MA1006 (manufactured by Nippon Shokubai Co., Ltd.), Taftic FH-S005 (manufactured by Nippon Exelan Industry 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 & Engineering Co., Ltd.), Tech Polymer 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 Chemical Co., Ltd.), etc.

[0165] Examples of commercially available products (styrene-acrylic particles) include Eposter MA2003 (manufactured by Nippon Shokubai Co., Ltd.), Tech Polymer MSX, SMX (manufactured by Sekisui Chemical Co., Ltd.), etc.

[0166] Examples of commercially available products (polystyrene particles) include Tech Polymer SBX-4 (manufactured by Sekisui Chemical Co., Ltd.), Chemisnow SX-130H, SX-350H, SX-500H (manufactured by Soken Chemical & Engineering Co., Ltd.), etc.

[0167] Examples of commercially available products (polyacrylonitrile particles) include Taftic ASF (manufactured by Nippon Exelan Industry Co., Ltd.), etc.

[0168] Commercially available products (melamine particles) include, for example, Epistar SS, Epistar S, Epistar FS, Epistar S6, Epistar S12 (manufactured by Nippon Shokubai Co., Ltd.), and the like.

[0169] Commercially available products (polyethylene particles) include, for example, Mipelon XM-220, XM221U (manufactured by Mitsui Chemicals, Inc.), Flow Beads LE-1080 (manufactured by Sumitomo Seika Chemicals Co., Ltd.), ChemPearl W500 (manufactured by Mitsui Chemicals, Inc.), and the like.

[0170] Commercially available products (benzoguanamine particles) include, for example, Epistar MS, M05, L15 (manufactured by Nippon Shokubai Co., Ltd.), and the like.

[0171] Manufacturing methods (organic particles) include, for example, the nozzle vibration method, the SPG membrane emulsification method, the microchannel method, the soap-free emulsion polymerization method, the dispersion polymerization method, the suspension polymerization method, the seed emulsion polymerization method, and the like.

[0172] (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, and the like. In one embodiment, the particle size preferably selects 5 nm to 100 nm. The reasons for the preference include, for example, hardness, flexibility, and the like.

[0173] 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, and the like. In one embodiment, the particle size preferably selects 0.5 μm to 10 μm. The reasons for the preference include, for example, improvement of anti-glare performance and the like.

[0174] "Particle size" refers to the volume average particle size. "Volume average particle size" refers to the particle size when the cumulative particle size distribution (volume basis) from the small particle size side is 50% for the volume-based particle size distribution measured by the dynamic light scattering method.

[0175] The volume-based particle size distribution can be measured through the following process. <Inorganic fine particles> (1) Preparation of the measurement solution A solution is prepared by adding the measurement sample (particles) to propylene glycol monomethyl ether (hereinafter referred to as PGME. For example, manufactured by Nippon Emulsifier Co., Ltd.) so that the concentration of the measurement sample is 1% by mass. (2) Measurement of particle size distribution based on volume Measuring instrument: Dynamic light scattering particle size distribution measuring device "LB-550" (HORIBA, Ltd.) Number of measurements: 5 Measurement temperature: 25 ± 0.5 °C Measurement time: 60 seconds Upper limit of measurement: 6000 nm Lower limit of measurement: 1 nm Measurement solvent: Refractive index of PGME: 1.404 <Organic particles> (1) Measurement of particle size distribution based on volume Measuring instrument: "Microtrac MT3000II" (Microtrac BEL) Number of measurements: 2 Measurement temperature: Room temperature Measurement time: 30 seconds Upper limit of measurement: 1400 μm Lower limit of measurement: 0.2 μm Measurement solvent: Refractive index of PGME: 1.404 In addition, the refractive index of the measurement sample (particles) can refer to reference values ("A GUIDE FOR ENTERING MICROTRAC" RUN INFORMATION "(F3) DATA", manufactured by Leeds & Northrup Co., Ltd.) and so on.

[0176] Refractive index (inorganic particles) such as 2.5, 2.3, 2.1, 2.0, 1.9, 1.7, 1.5, 1.3, 1.2, etc. are given. In one embodiment, the refractive index is preferably selected from 1.2 to 2.5.

[0177] Refractive index (organic particles) such as 1.65, 1.63, 1.61, 1.60, 1.59, 1.57, 1.55, 1.53, 1.51, 1.50, 1.49, etc. are given. In one embodiment, the refractive index is preferably selected from 1.49 to 1.65.

[0178] The refractive index is measured according to the following conditions. Standard: JIS K 7142 (1996)

[0179] Particle shapes such as spherical, hollow, solid, porous, rod-shaped, plate-shaped, fibrous, irregular shapes, etc. are given.

[0180] Particles such as hydrophilic particles, hydrophobic particles, etc. are given.

[0181] The mass% content (particles / non-volatile components of the active energy ray curable composition) 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 selected from 0 mass% to 85 mass%, and more preferably from 0 mass% to 40 mass%.

[0182] The mass% content (inorganic particles / non-volatile components of the active energy ray curable composition) 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 selected from 0 mass% to 85 mass%, and more preferably from 0 mass% to 40 mass%.

[0183] The mass% content (organic particles / non-volatile components of the active energy ray curable composition) 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 selected from 0 mass% to 30 mass%, and more preferably from 0 mass% to 20 mass%.

[0184] <Polymer> In one embodiment, the active energy ray curable composition may optionally contain a polymer. The polymer can be used alone or in combination of two or more.

[0185] (Non-polar monomer unit) The polymer may contain non-polar monomer units. The non-polar monomers can be used alone or in combination of two or more.

[0186] Examples of the non-polar monomers include unsubstituted alkyl (meth)acrylates, vinyl aromatic compounds, etc.

[0187] Examples of the unsubstituted alkyl (meth)acrylates include unsubstituted linear alkyl (meth)acrylates, unsubstituted branched alkyl (meth)acrylates, unsubstituted cycloalkyl (meth)acrylates, etc.

[0188] (Meth)acrylic acid unsubstituted linear alkyl esters include, for example, 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, palmitic (meth)acrylate, heptadecyl (meth)acrylate, stearic (meth)acrylate, etc.

[0189] (Meth)acrylic acid unsubstituted branched alkyl esters include, for example, isopropyl (meth)acrylate, isobutyl (meth)acrylate, isopentyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, etc.

[0190] (Meth)acrylic acid unsubstituted cycloalkyl esters include, for example, cyclohexyl (meth)acrylate, etc.

[0191] Vinyl aromatic compounds include, for example, styrene, α-methylstyrene, p-methylstyrene, vinyltoluene, divinylbenzene, etc.

[0192] 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%.

[0193] The mole% content (non-polar monomer unit / polymer) includes, for example, 99 mole%, 96 mole%, 95 mole%, 90 mole%, 85 mole%, 80 mole%, 75 mole%, 70 mole%, 65 mole%, 60 mole%, 55 mole%, 50 mole%, 45 mole%, 40 mole%, 35 mole%, 30 mole%, 25 mole%, 20 mole%, 15 mole%, 10 mole%, 5 mole%, 0 mole%, etc. In one embodiment, the content is preferably 0 mole% to 99 mole%, more preferably 50 mole% to 99 mole%, and further preferably 65 mole% to 96 mole%. The reasons for preference include, for example, improved leveling property, improved compatibility, etc.

[0194] (Monomer unit containing a hydroxyl group) The polymer may contain hydroxy-containing monomer units. The hydroxy-containing monomers may be used alone or in combination of two or more.

[0195] Examples of the hydroxy-containing monomers include hydroxy-containing (meth)acrylates, hydroxy-containing vinyl ethers, etc.

[0196] Examples of the hydroxy-containing (meth)acrylates include linear hydroxy-containing (meth)acrylates, branched hydroxy-containing (meth)acrylates, etc.

[0197] Examples of the linear hydroxy-containing (meth)acrylates include 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, etc.

[0198] Examples of the branched hydroxy-containing (meth)acrylates 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, 1,1-dimethyl-2-hydroxyethyl (meth)acrylate, etc.

[0199] Examples of the hydroxy-containing vinyl ethers include hydroxyalkyl vinyl ethers, polyalkylene glycol mono vinyl ethers, etc.

[0200] Examples of the hydroxyalkyl vinyl ethers include linear hydroxyalkyl vinyl ethers, branched hydroxyalkyl vinyl ethers, cycloalkyl hydroxyalkyl vinyl ethers, etc.

[0201] Examples of the polyalkylene glycol mono vinyl ethers include polymethylene glycol mono vinyl ether, polyethylene glycol mono vinyl ether, polypropylene glycol mono vinyl ether, etc.

[0202] The mass% content (hydroxy-containing monomer unit / 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 still more preferably 5 mass% to 30 mass%.

[0203] The molar percentage content (hydroxyl group-containing monomer unit / 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 selected from 0 mol% to 40 mol%, and more preferably from 4 mol% to 35 mol%. The reasons for preference include, for example, improved leveling property, improved compatibility, etc.

[0204] (Unsaturated carboxylic acid (salt) unit) In one embodiment, the polymer may optionally contain unsaturated carboxylic acid (salt) units. The unsaturated carboxylic acid (salt) can be used alone or in combination of two or more.

[0205] Examples of the unsaturated carboxylic acid include (meth)acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, etc.

[0206] Examples of the unsaturated carboxylate include inorganic salts of unsaturated carboxylic acids, organic salts of unsaturated carboxylic acids, etc.

[0207] Examples of the inorganic salt of unsaturated carboxylic acid include sodium unsaturated carboxylate, lithium unsaturated carboxylate, calcium unsaturated carboxylate, ammonium unsaturated carboxylate, etc.

[0208] Examples of the organic salt of unsaturated carboxylic acid include amine unsaturated carboxylate, etc.

[0209] The mass percentage content (unsaturated carboxylic acid (salt) unit / polymer) includes, for example, 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 selected from 0 mass% to 30 mass%.

[0210] The molar percentage content (unsaturated carboxylic acid (salt) unit / polymer) includes, for example, 38 mol%, 35 mol%, 30 mol%, 25 mol%, 20 mol%, 15 mol%, 10 mol%, 5 mol%, 2 mol%, 1 mol%, 0 mol%, etc. In one embodiment, the content is preferably selected from 0 mol% to 38 mol%.

[0211] (Other structural units) The polymer may optionally contain structural units other than non-polar monomer units, hydroxyl group-containing monomer units, and unsaturated carboxylic acid (salt) units (other structural units).

[0212] Examples of the monomers other than those mentioned above include (meth)acrylamide, (meth)acrylonitrile, polyfunctional (meth)acrylate, etc.

[0213] Examples of polyfunctional (meth)acrylates include ethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, etc.

[0214] 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%, 0 mass%, etc.

[0215] Examples of the mass% content (other structural units / any one of the non-polar monomer units, hydroxyl group-containing monomer units, unsaturated carboxylic acid (salt) units) include less than 10 mass%, less than 5 mass%, less than 2 mass%, less than 1 mass%, less than 0.1 mass%, 0 mass%, etc.

[0216] Examples of the mole% content (other structural units / polymer) include less than 10 mole%, less than 5 mole%, less than 2 mole%, less than 1 mole%, less than 0.1 mole%, 0 mole%, etc.

[0217] Examples of the mole% content (other structural units / any one of the non-polar monomer units, hydroxyl group-containing monomer units, unsaturated carboxylic acid (salt) units) include less than 10 mole%, less than 5 mole%, less than 2 mole%, less than 1 mole%, less than 0.1 mole%, 0 mole%, etc.

[0218] <Physical properties, etc. (polymer)> The glass transition temperature (polymer) is, for example, 190 °C, 185 °C, 180 °C, 170 °C, 160 °C, 15 0 °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 above glass transition temperature is preferably 50 °C to 190 °C, more preferably 90 °C to 190 °C.

[0219] The glass transition temperature is measured under the following conditions. Differential scanning calorimeter: Product name "DSC8230B", manufactured by Rigaku Corporation Heating rate: 10 °C / min

[0220] When the input amount of the monomer used in manufacturing the polymer can be accurately grasped and the polymerization rate is high, the glass transition temperature is calculated by Fox's formula. Fox's 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 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)

[0221] Hydroxyl value (polymer), for example, 175 mg KOH / g, 172 mg KOH / g, 170 mg KOH / g, 165 mg KOH / g, 160 mg KOH / g, 155 mg KOH / g, 150 mg KOH / g, 145 mg KOH / g, 140 mg KOH / g, 135 mg KOH / g, 130 mg KOH / g, 125 mg KOH / g, 120 mg KOH / g, 115 mg KOH / g, 110 mg KOH / g, 105 mg KOH / g, 100 mg KOH / g, 95 mg KOH / g, 90 mg KOH / g, 85 mg KOH / g, 80 mg KOH / g, 75 mg KOH / g, 70 mg KOH / g, 65 mg KOH / g, 60 mg KOH / g, 55 mg KOH / g, 50 mg KOH / g, 45 mg KOH / g, 44 mg KOH / g, 41 mg KOH / g, 40 mg KOH / g, 35 mg KOH / g, 30 mg KOH / g, 25 mg KOH / g, 22 mg KOH / g, 20 mg KOH / g, 15 mg KOH / g, 10 mg KOH / g, 5 mg KOH / g, 4 mg KOH / g, etc. In one embodiment, the hydroxyl value is preferably selected from 4 mg KOH / g to 175 mg KOH / g, and more preferably from 30 mg KOH / g to 175 mg KOH / g.

[0222] The hydroxyl value can be measured by a method based on Japanese Industrial Standard (JIS) K0070 (neutralization titration method).

[0223] When the input amount of the monomer used in the production of the polymer can be accurately grasped and the polymerization rate is high, the hydroxyl value can be calculated by the following formula. Hydroxyl value = [(Input mass of hydroxyl group-containing monomer in 1 g of all input monomers × Number of hydroxyl groups in one molecule of hydroxyl group-containing monomer) / Molecular weight of hydroxyl group-containing monomer] × 56.11 (Molecular weight of KOH) × 1000

[0224] Examples of the acid value (polymer) include 250 mg KOH / g, 225 mg KOH / g, 200 mg KOH / g, 175 mg KOH / g, 150 mg KOH / g, 125 mg KOH / g, 100 mg KOH / g, 75 mg KOH / g, 50 mg KOH / g, 25 mg KOH / g, 20 mg KOH / g, 10 mg KOH / g, 4 mg KOH / g, etc. In one embodiment, the acid value is preferably selected from 4 mg KOH / g to 250 mg KOH / g.

[0225] The acid value is measured by a method (neutralization titration method) based on JIS K0070.

[0226] (Meth)acrylic acid equivalent, for example, includes 800 g / eq, 775 g / eq, 750 g / eq, 725 g / e q, 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 reasons for the preference include, for example, reducing the curl (bending) of the cured product while achieving antiglare performance and mechanical properties, etc.

[0227] The “(meth)acrylic acid equivalent” refers to the calculated value (g / eq) of the mass per 1 mole of (meth)acryloyl group.

[0228] Weight-average molecular weight: Mw (of the polymer) is, for example, 400,000, 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, 25,000, etc. In one embodiment, the weight-average molecular weight is preferably 25,000 to 400,000, more preferably 37,500 to 150,000, and still more preferably 50,000 to 100,000. The reasons for the preference are, for example, improved leveling property, etc.

[0229] Number-average molecular weight: Mn (of the polymer) is, for example, 100,000, 80,000, 60,000, 55,000, 54,000, 50,000, 45,000, 40,000, 35,000, 30,000, 28,000, 27,000, 25,000, 23,000, 21,000, 20,000, 19,000, 17,000, 15,000, 14,000, 12,000, 10,000, 9,000, 8,750, 8,500, etc. In one embodiment, the number-average molecular weight is preferably 8,500 to 100,000, more preferably 14,000 to 35,000, and still more preferably 15,000 to 30,000. The reasons for the preference are, for example, improved leveling property, etc.

[0230] Molecular weight distribution: Mw / Mn (of the 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 still more preferably 2.5 to 4.2. The reasons for the preference are, for example, improved leveling property, etc.

[0231] The measurement conditions for the weight-average molecular weight and the number-average molecular weight are, for example, the following conditions, etc. · Measuring machine: manufactured by Tosoh Corporation, GPC (model: HLC-8420) · Column: Product name "TSKgel SuperHZM-M" (TOSOH) × 3 columns · Eluent: tetrahydrofuran · Column temperature: 40 °C · Calibration curve: monodisperse polystyrene · Detector: refractive index (RI) · Concentration of polymer: 1% by mass · Measuring method: Measured after filtration through a filter.

[0232] (Manufacturing method (polymer)) Examples of the manufacturing method (polymer) include radical polymerization and the like.

[0233] The radical polymerization initiator can be used alone or in combination of two or more. Examples of the radical polymerization initiator include inorganic peroxides, organic peroxides, azo compounds, etc.

[0234] Examples of inorganic peroxides include hydrogen peroxide, ammonium persulfate, potassium persulfate, etc.

[0235] Examples of organic peroxides include benzoyl peroxide, dicumyl peroxide, lauroyl peroxide, etc.

[0236] Examples of azo compounds include 2,2'-azobisisobutyronitrile, dimethyl 2,2'-azobis(2-methylpropionate), etc.

[0237] The usage amount by mass (radical polymerization initiator / total monomer components) preferably selects 0.1 part by mass to 5 parts by mass.

[0238] In the production of the polymer, a chain transfer agent can be optionally used. The chain transfer agent can be used alone or in combination of two or more.

[0239] Examples of the chain transfer agent include lauryl mercaptan, dodecyl mercaptan, 2-mercaptobenzothiazole, bromotrichloromethane, α-methylstyrene dimer, etc.

[0240] The usage amount by mass (chain transfer agent / total monomer components) preferably selects 0 part by mass to 5 parts by mass.

[0241] The mass% content (polymer / non-volatile components of the active energy ray curable composition) includes, for example, 20% by mass, 19% by mass, 17% by mass, 15% by mass, 13% by mass, 11% by mass, 10% by mass, 9% by mass, 7% by mass, 5% by mass, 3% by mass, 1% by mass, 0% by mass, etc. In one embodiment, the content preferably selects 0% by mass to 20% by mass.

[0242] In one embodiment, the mass part content [polymer / (triple or more (ethylenically unsaturated) compounds without urethane bonds and poly (ethylenically unsaturated) compounds containing urethane bonds)] preferably selects less than 50 parts by mass, and more preferably selects 15 parts by mass or less. The reasons for preference include, for example, improvement of scratch resistance, improvement of pencil hardness, etc. <Photoinitiator> In one embodiment, the energy ray curable composition may optionally contain a photopolymerization initiator. The photopolymerization initiator may be used alone or in combination of two or more.

[0243] Examples of the photopolymerization initiator include photopolymerization initiators containing an α-hydroxy dimethylacetophenone group, α-hydroxy cycloalkyl ketones, α-amino alkyl ketones, benzil dimethyl ketal, unsubstituted or substituted benzyl ketones, unsubstituted or substituted benzil (benzyl), unsubstituted or substituted benzophenones, acylphosphine oxides, substituted thioxanthones, oxime esters, and the like.

[0244] Examples of the photopolymerization initiator containing an α-hydroxy dimethylacetophenone group include 2-hydroxy-2-methyl-1-phenylpropanone, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methylpropanone, 2-hydroxy-1-(4-(4-(2-hydroxy-2-methylpropanoyl)benzyl)phenyl)-2-methylpropan-1-one, and the like.

[0245] Examples of α-hydroxy cycloalkyl ketones include 1-hydroxycyclohexyl phenyl ketone and the like.

[0246] Examples of α-amino alkyl ketones include 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one and the like.

[0247] Examples of benzil dimethyl ketal include 2,2-dimethoxy-1,2-diphenylethane-1-one and the like.

[0248] Examples of unsubstituted or substituted benzyl ketones 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-isonitrosoacetophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, and the like.

[0249] Examples of unsubstituted or substituted benzil include benzil, anisil (p-anisyl), and the like.

[0250] 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, methyl 2-benzoylbenzoate, and the like.

[0251] Examples of acylphosphine oxides include 2,4,6-trimethylbenzoyl-diphenyl-oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, and the like.

[0252] Examples of substituted thioxanthones include 2-chlorothioxanthone, 2-isopropylthioxanthone, 2,4-diethylthioxanthone, and the like.

[0253] Examples of oxime esters include 1,2-octanedione, 1-[4-(phenylthio)-, 2-(o-benzoyloximato)] (1,2-octanedione, 1-[4-(phenylthio)-, 2-(O-benzoyloximato)]) (i.e., 2-((benzoyloxy)imino)-1-(4-(phenylthio)phenyl)octan-1-one); Ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(o-acetylimino) (ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetylimino)) (i.e., 1-(((1-(9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl)ethylidene)amino)oxy)ethan-1-one) and the like.

[0254] When electron beam curing is carried out, a photoinitiator is not required.

[0255] The mass% content (photoinitiator / non-volatile components of the active energy ray curable composition) 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%, and the like. In one embodiment, the content is preferably 0 mass% to 10 mass%, and more preferably 1 mass% to 6 mass%.

[0256] <Inhibitor> In one embodiment, the active energy ray curable composition may optionally contain an inhibitor. The inhibitor can be used alone or in combination of two or more.

[0257] Examples of the inhibitor include hindered phenols and the like.

[0258] "Hindered phenol" refers to a compound having "a phenyl group in which a tert-butyl group is bonded to a carbon atom adjacent to the carbon atom to which the phenolic hydroxyl group is bonded".

[0259] Examples of hindered phenols include monohindered phenols.

[0260] "Monohindered phenol" refers to a compound having 1 "phenyl group in which a tert-butyl group is bonded to a carbon atom adjacent to the carbon atom to which the phenolic hydroxyl group is bonded".

[0261] Examples of monohindered phenols include 2,6-di-tert-butyl-p-cresol and the like.

[0262] In one embodiment, the polymerization inhibitor is preferably a hindered phenol, more preferably a mono-hindered phenol, and even more preferably 2,6-di-tert-butyl-p-cresol. The reasons for the preference include, for example, the improvement of the stability of the coating.

[0263] The mass% content (polymerization inhibitor / non-volatile component of the active energy ray curable composition) 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%, etc. In one embodiment, the content is preferably 0.01 mass% to 0.2 mass%.

[0264] <Organic solvent> In one embodiment, the active energy ray curable composition may optionally contain an organic solvent. The organic solvent can be used alone or in combination of two or more.

[0265] Examples of the organic solvent include ketone solvents, aromatic solvents, alcohol solvents, glycol solvents, glycol ether solvents, ester solvents, petroleum solvents, halogenated alkane solvents, amide solvents, etc.

[0266] Examples of the ketone solvent include methyl ethyl ketone, acetylacetone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, etc.

[0267] Examples of the aromatic solvent include toluene, xylene, etc.

[0268] Examples of the alcohol solvent include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, etc.

[0269] Examples of the glycol solvent include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, polyethylene glycol, polypropylene glycol, etc.

[0270] 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 monon-propyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monon-butyl ether, ethylene glycol monoisobutyl ether, ethylene glycol monoter-butyl ether, etc.

[0271] Examples of the ester solvent include ethyl acetate, butyl acetate, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, etc.

[0272] Examples of the petroleum solvent include Solvesso #100 (manufactured by Exxon), Solvesso #150 (manufactured by Exxon), etc.

[0273] Examples of the halogenated alkane solvents include chloroform and the like.

[0274] Examples of the amide solvents include dimethylformamide and the like.

[0275] In one embodiment, the organic solvent is preferably selected from alcohol solvents and glycol ether solvents, more preferably isopropyl alcohol, n-butanol, isobutanol, propylene glycol monomethyl ether, and further preferably the combined use of isopropyl alcohol and propylene glycol monomethyl ether, the combined use of n-butanol and propylene glycol monomethyl ether, and particularly preferably the combined use of isopropyl alcohol and propylene glycol monomethyl ether. Examples of the preferred reasons include improved leveling property and the like.

[0276] The mass% content (organic solvent / active energy ray curable composition) is, 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 selected from 0 mass% to 99 mass%.

[0277] <Additive> The active energy ray curable composition may optionally contain a reagent (additive) that does not belong to any of the above.

[0278] Examples of the additives include ultraviolet absorbers, defoamers, surface conditioners, anti-pollution agents, pigments, etc.

[0279] In one embodiment, the parts by mass 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, 0 part by mass, etc.

[0280] In one embodiment, the parts by mass content (additive / di(ethylenically unsaturated) compound without a urethane bond), the parts by mass content (additive / poly(ethylenically unsaturated) compound with a urethane bond), the parts by mass content (additive / tri or more (ethylenically unsaturated) compound without a urethane bond) 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.

[0281] The active energy ray curable composition can be produced by dispersing and mixing the above-mentioned reagents.

[0282] Examples of the dispersion and mixing means include an emulsifying disperser, an ultrasonic dispersing device, etc.

[0283] Uses (actinic energy ray curable composition) include, for example, coating agents, hard coating agents, transparent coating agents, transparent hard coating agents, anti-glare coating agents, anti-glare hard coating agents, coating agents for optical films, hard coating agents for optical films, coating agents for acrylic substrates, hard coating agents for acrylic substrates, anti-glare coating agents for acrylic substrates, anti-glare hard coating agents for acrylic substrates, etc.

[0284] Specific examples of the composition of the actinic energy ray curable composition include the following compositions, etc. The numbers in the table represent parts by mass. In addition, in the examples, the components in the table are described.

[0285]

Table EX1

Table EX2

Table EX3

Table EX4

Table EX5

Table EX6

Table EX7

Table EX8

Table EX9

[0286] [Cured product] This disclosure relates to a cured product of the actinic energy ray curable composition.

[0287] Curing conditions include, for example, the following conditions, etc.

[0288] [Laminate] This disclosure relates to a laminate comprising the cured product.

[0289] Manufacturing methods (laminate) include, for example, the following process methods, etc. Actinic energy ray curable composition coating step: A step of coating the actinic energy ray curable composition on at least one surface of a substrate. Actinic energy ray curing step: A step of forming a cured product layer of the actinic energy ray curable composition by irradiating actinic energy rays.

[0290] Examples of the base material include a polycarbonate film, an acrylic film (such as a polymethyl methacrylate film), a polystyrene film, a polyester film, a polyolefin film, an epoxy resin film, a melamine resin film, a triacetyl cellulose film, an ABS film, an AS film, a norbornene-based resin film, a cyclic olefin film, a polyvinyl alcohol film, and the like.

[0291] In one embodiment, the thickness (of the base material) is preferably selected from 10 μm to 2000 μm.

[0292] In one embodiment, the thickness (of the cured product layer) is preferably selected from 0.05 μm to 20 μm.

[0293] (Coating step) 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, screen printing method, and the like.

[0294] (Active energy ray curing step) Examples of the active energy ray include ultraviolet rays, electron beams, and the like.

[0295] Examples of the ultraviolet light source include a xenon lamp, a high-pressure mercury lamp, a metal halide lamp, and the like.

[0296] In the case of using a high-pressure mercury lamp, the curing conditions are preferably selected from the following conditions and the like. Lamp output: 25 W / cm to 160 W / cm UV illuminance: 10 mW / cm2 to 800 mW / cm2 Accumulated light quantity: 25 mJ / cm2 to 2000 mJ / cm2 Conveyor speed: 1 m / minute to 50 m / minute

[0297] In the case of using an electron beam, the curing conditions are preferably selected from the following conditions and the like. Accelerating voltage: 10 kV to 300 kV Conveyor speed: 5 m / minute to 50 m / minute [Examples]

[0298] Hereinafter, the present invention will be specifically described by way of examples and comparative examples. However, the above description and the following examples are not described for the purpose of limiting the present invention. The present invention is only limited by the scope of the claims. Hereinafter, unless otherwise specified, values such as parts and % are based on mass.

[0299] Production Example 1-1: Polymer In a four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer, and a dropping funnel, into a reaction vessel containing 0.5 part of 2,2'-azobis(2-methylbutyronitrile) as a polymerization initiator and 186 parts of propylene glycol monomethyl ether (PGME), while dropping the monomers described in the following table, the reaction was carried out at 80 °C for 2 hours. After 2 hours, 1 part of 2,2'-azobis(2-methylbutyronitrile) was added, and the reaction was carried out for 3 hours to obtain a polymer (non-volatile component concentration: 30%).

[0300] Unless otherwise specified, except for the changes as shown in the following table, other examples were carried out in the same manner as above.

[0301]

Table 1

[0302] Production Examples 1-3 Into a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen gas 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, and stirring was carried out. The temperature was raised to 85 °C under a nitrogen gas stream, and then the reaction was carried out for 10 hours. After the reaction was completed, it was cooled to 60 °C, 50 parts of acrylic acid, 0.1 part of triphenylphosphine, and 0.05 part of p-methoxyphenol were added. The nitrogen gas inlet was replaced with an air bubbling device, and while air was bubbled through the reaction solution, stirring was carried out, the temperature was raised to 110 °C, and a heat preservation reaction was carried out 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).

[0303] 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 Denki Co., Ltd. Heating rate: 10 °C / min

[0304] The weight average molecular weight, number average molecular weight, and molecular weight distribution were measured under the following conditions. · Measuring instrument: Manufactured by Tosoh Corporation, GPC (model: HLC-8420) · Column: "TSKgel SuperHZM-M" (manufactured by Tosoh Corporation) × 3 pieces · Eluent: Tetrahydrofuran · Column temperature: 40 °C · Calibration curve: Monodisperse polystyrene · Detector: Refractive index (RI) · Concentration of polymer: 1% by mass · Measurement method: Measured after filtration through a filter.

[0305] Production Example 2-1: Poly(ethylenically unsaturated) compound containing a urethane bond After charging the raw materials described in the following table and 0.05 part of stannous octoate into a reaction vessel equipped with a stirring device and a condenser tube, the temperature of the system was raised to about 80 °C over about 1 hour. Next, the reaction system was maintained at the same temperature for 2 hours and then cooled to obtain a poly(ethylenically unsaturated) compound containing a urethane bond.

[0306] Unless otherwise specified, except for the changes as shown in the following table, other examples were carried out in the same manner as above.

[0307]

Table 2

[0308] Example 1: Actinic energy ray curable composition After mixing the substances described in the following table as non-volatile components and diluting with PGME, an actinic energy ray curable composition (non-volatile component 30%) was obtained.

[0309] Unless otherwise specified, except for the changes as shown in the following table, other examples were carried out in the same manner as above.

[0310]

Table 3

[0311] (Laminate) A curable composition using active energy rays was applied to a substrate under the following conditions. Then, the coated material was dried under the following conditions. Subsequently, the dried material was cured under the following conditions to obtain a laminate. · Coating conditions Substrate: Acrylic film (40 μm), manufactured by Okura Industries Co., Ltd. Coating method: Rod coater, model "No. 11", manufactured by RD SPECIALTIES Film thickness: Approximately 5 μm · Drying conditions 95 °C, 1 minute (in a circulating air dryer) · Curing conditions Irradiation distance: 20 cm Belt speed: 5 m / min Cumulative irradiation dose: 190 mJ / cm 2 Under a nitrogen atmosphere (oxygen concentration 400 ppm or less)

[0312] (Adhesiveness) A 100-grid test was carried out using an Elpack LP-24 (24 mm wide) tape manufactured by Nichiban Co., Ltd. (tested 3 times at the same position). 5B: No peeling 4B: Edge breakage occurs or delamination occurs in less than 5% of the test area 3B: Delamination occurs in more than 5% and less than 15% of the test area 2B: Delamination occurs in more than 15% and less than 35% of the test area 1B: Delamination occurs in more than 35% and less than 65% of the test area 0B: Delamination occurs in more than 65% of the test area.

Claims

1. A curable composition for active energy rays, The curable composition for active energy rays contains: a bis(ethylenically unsaturated) compound having no urethane bond and a poly(ethylenically unsaturated) compound having a urethane bond, The bis(ethylenically unsaturated) compound having no urethane bond has a molecular weight of 260 or less.

2. The curable composition for active energy rays according to claim 1, which contains particles.

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

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

Images