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

Abstract

To provide an active energy ray-curable composition, a cured product, and a laminate.SOLUTION: The active energy ray-curable composition contains a urethane bond-free di(ethylenically unsaturated) compound and a urethane bond-containing poly(ethylenically unsaturated) compound. The molecular weight of the urethane bond-free di(ethylenically unsaturated) compound is 260 or less.SELECTED DRAWING: None

Description

Technical Field

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

Background Art

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

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems 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 with good adhesion.

Means for Solving the Problems

[0005] The following items are provided by the present disclosure. (Item 1) An active energy ray curable composition, wherein the active energy ray curable composition contains a urethane bond-free di(ethylenically unsaturated) compound and a urethane bond-containing poly(ethylenically unsaturated) compound, and the molecular weight of the urethane bond-free di(ethylenically unsaturated) compound is 260 or less. Active energy ray curable composition. (Item 2) The active energy ray curable composition according to the above item, containing 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 of the above-described features may be provided in combination in addition to the explicitly stated combinations.

Advantages of the Invention

[0007] The cured product of the present invention exhibits good adhesion.

Modes for Carrying Out the Invention

[0008] Throughout the present disclosure, the ranges of numerical values such as each physical property value and content can be set as appropriate (for example, selected from the values described in each of the following items). Specifically, for the numerical value α, when A3, A2, A1 (where A3 > A2 > A1) etc. are listed, the range of the numerical value α is 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, each component, condition, numerical value etc. are not particularly limited.

[0010] "The amount of αβ (A / B)" means the β amount (α) of A with respect to 100α of B. α includes, for example, mass%, mol%, parts by mass etc. The β amount includes, for example, content, usage amount etc. "Mass% content (A / B)" means the content (mass%) of A with respect to 100 mass% of B.

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

[0012] "Non-volatile content" means the total mass of components other than organic solvents and water.

[0013] "(Meth)acryl" means "acryl and / or methacryl". "(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 group" means an alkyl group having 1 to 6 carbon atoms. "C6 alkyl group" means an alkyl group having 6 carbon atoms.

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

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

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

[0019] Examples of the cycloalkyl group include a monocyclic cycloalkyl group, a bridged-ring cycloalkyl group, a condensed-ring cycloalkyl group, etc. Note that 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 ring" means a cyclic structure formed by covalent bonds of carbon atoms and having no bridging structure inside. "Fused ring" means a cyclic structure in which two or more monocyclic rings share two atoms (that is, each ring shares only one side with each other (fused)). "Bridged ring" means a cyclic structure in which two or more monocyclic rings share three or more atoms.

[0021] Examples of the monocyclic cycloalkyl group include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclodecyl group, a 3,5,5-trimethylcyclohexyl group, and the like.

[0022] Examples of the bridged ring cycloalkyl group include a tricyclodecyl group, an adamantyl group, a norbornyl group, and the like.

[0023] Note that the alkyl group includes a linear alkyl group, a branched alkyl group, and a group formed by combining a cycloalkyl group. Examples of the combined group include a cycloalkylalkyl group and the like.

[0024] The cycloalkylalkyl group 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 the alkylene group include a linear alkylene group, a branched alkylene group, a cycloalkylene group, and the like.

[0026] Examples of the linear alkylene group include a methylene group, an ethylene group, an n-propylene group, an n-butylene group, an n-pentylene group, an n-hexylene group, an n-heptylene group, an n-octylene group, an n-nonylene group, an n-decamethylene group, and the like.

[0027] Examples of the branched alkylene group include a diethylpentylene group, a trimethylbutylene group, a trimethylpentylene group, a trimethylhexylene group, and the like.

[0028] Examples of the cycloalkylene group include a monocyclic cycloalkylene group, a bridged cycloalkylene group, a fused cycloalkylene group, etc. The cycloalkylene group may have one or more hydrogen atoms substituted by a linear or branched alkyl group.

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

[0030] Examples of the bridged cycloalkylene group include a tricyclodecylene group, an adamantylene group, a norbornylene group, etc.

[0031] Examples of the fused cycloalkylene group include a bicyclodecylene group, etc.

[0032] Note that the alkylene group also includes a group formed by combining a linear alkylene group, a branched alkylene group, and a cycloalkylene group. Examples of the combined group include a cycloalkylenealkylene group, an alkylene cycloalkylene alkylene group, etc.

[0033] The cycloalkylenealkylene 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 alkylene cycloalkylene alkylene 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 or may not be substituted. Examples of the substituent of the aromatic group include an alkyl group, a thioalkyl group, a thioaryl group, a carbonylaryl group, etc.

[0036] Examples of the aryl group include a monocyclic aryl group, a condensed-ring aryl group, etc.

[0037] Examples of the monocyclic aryl group include a phenyl group, a tolyl group, a mesityl group, etc.

[0038] Examples of the condensed-ring aryl group include a naphthyl group, etc.

[0039] Examples of the arylene group include a monocyclic arylene group, a condensed-ring arylene group, etc.

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

[0041] Examples of the condensed-ring arylene group include a naphthylene group, etc.

[0042] [Active energy ray curable composition: Composition] The present disclosure relates to an active energy ray curable composition, wherein the active energy ray curable composition contains a urethane bond-free di(ethylenically unsaturated) compound and a urethane bond-containing poly(ethylenically unsaturated) compound, and the molecular weight of the urethane bond-free di(ethylenically unsaturated) compound is 260 or less. It relates to an active energy ray curable composition.

[0043] [Urethane bond-free di(ethylenically unsaturated) compound] The urethane bond-free di(ethylenically unsaturated) compound can be used alone or in combination of two or more.

[0044] "Urethane bond-free di(ethylenically unsaturated) compound" means a urethane bond-free compound having two ethylenically unsaturated bonds.

[0045] Examples of the ethylenically unsaturated bond-containing group include a (meth)acryloyl group, a (meth)allyl group, a vinyl group, and the like.

[0046] Examples of the urethane bond-free di(ethylenically unsaturated) compound include (poly)alkylene diol di(meth)acrylate, a (meth)acrylate containing a vinyl ether group, and the like.

[0047] In one embodiment, the (poly)alkylene diol di(meth)acrylate is represented by the following structural formula. [Chemical formula] (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 C1-8 alkylene group. when r = 1, R ad1 = R ad3 = methacryloyl group, R ad2 represents a C1-6 alkylene group. when r = 2, R ad1 = R ad3 = acryloyl group, R ad2 represents a C1-3 alkylene group. when r = 2, R ad1 = R ad3 = methacryloyl group, R ad2 represents a C1-2 alkylene group.

[0048] (Poly)alkylene diol di(meth)acrylate includes, for example, alkylene diol diacrylate, alkylene diol dimethacrylate, polyalkylene diol diacrylate, polyalkylene diol dimethacrylate, etc. Examples of alkylene diol diacrylate include ethylene glycol diacrylate (molecular weight: 170), propane diol diacrylate (molecular weight: 184), butane diol diacrylate (molecular weight: 198), pentane diol diacrylate (molecular weight: 212), hexane diol diacrylate (molecular weight: 226), heptane diol diacrylate (molecular weight: 240), octane diol diacrylate (molecular weight: 254), nonane diol diacrylate (molecular weight: 268), neopentyl glycol diacrylate (molecular weight: 212), etc.

[0049] Examples of alkylene diol dimethacrylate include ethylene glycol dimethacrylate (molecular weight: 198), propane diol dimethacrylate (molecular weight: 212), butane diol dimethacrylate (molecular weight: 226), pentane diol dimethacrylate (molecular weight: 240), hexane diol dimethacrylate (molecular weight: 254), neopentyl glycol dimethacrylate (molecular weight: 240), etc.

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

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

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

[0053] The molecular weight (urethane bond-free di(ethylenically unsaturated) compound) is, 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 above molecular weight is preferably 260 or less, and more preferably 170 to 260.

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

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

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

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

[0058] <Hydroxyl group-containing poly(meth)acrylate> Examples of the hydroxyl group-containing poly(meth)acrylate include hydroxyl group-containing (poly)pentaerythritol poly(meth)acrylate, hydroxyl group-containing (poly)trimethylolpropane poly(meth)acrylate, hydroxyl group-containing (poly)glycerin poly(meth)acrylate, etc.

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

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

[0061] Examples of the polyisocyanate include linear aliphatic polyisocyanate, branched aliphatic polyisocyanate, alicyclic polyisocyanate, aromatic polyisocyanate, and their biuret compounds, isocyanurate compounds, allophanate compounds, adduct compounds, 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 diethyl pentylene diisocyanate, trimethyl butylene diisocyanate, trimethyl pentylene diisocyanate, trimethyl hexamethylene diisocyanate, etc.

[0064] Examples of the alicyclic polyisocyanate include monocyclic alicyclic polyisocyanate, crosslinked alicyclic polyisocyanate, condensed alicyclic polyisocyanate, etc.

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

[0066] Examples of the crosslinked alicyclic polyisocyanate include tricyclodecylene diisocyanate, adamantane diisocyanate, and norbornene diisocyanate.

[0067] An example of the condensed ring alicyclic polyisocyanate is bicyclodecylene diisocyanate.

[0068] Examples of aromatic polyisocyanates include monocyclic aromatic polyisocyanates and condensed ring aromatic polyisocyanates.

[0069] Examples of the monocyclic aromatic polyisocyanate include dialkyldiphenylmethane diisocyanates such as 4,4'-diphenyldimethylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanates such as 4,4'-diphenyltetramethylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-dibenzyl isocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, and m-tetramethylxylylene diisocyanate.

[0070] An example of the condensed ring aromatic polyisocyanate is 1,5-naphthylene diisocyanate.

[0071] In one embodiment, the urethane bond-containing poly(ethylenically unsaturated) compound preferably includes a urethane bond-containing poly(ethylenically unsaturated) compound having (poly)pentaerythritol poly(meth)acrylate as a constituent unit. More preferably, it includes a reaction product of (poly)pentaerythritol poly(meth)acrylate and any one of a urethane body, biuret body, and allophanate body of a linear aliphatic polyisocyanate. Even more preferably, it includes a reaction product of (poly)pentaerythritol poly(meth)acrylate and any one of a urethane body and biuret body of hexamethylene diisocyanate.

[0072] The weight average molecular weight: Mw (urethane bond-containing poly(ethylenically unsaturated) compound) is, for example, 150000, 120000, 100000, 80000, 60000, 50000, 40000, 30000, 20000, 15000, 10000, 9000, 8000, 7000, 6000, 5000, 4000, 3000, 2000, 1500, etc. In one embodiment, the above weight average molecular weight is preferably 1500 to 150000, and more preferably 2000 to 20000. The reasons for preference include, for example, improvement in leveling property.

[0073] The number average molecular weight: Mn (urethane bond-containing poly(ethylenically unsaturated) compound) is, for example, 30000, 20000, 15000, 10000, 9000, 8000, 7000, 6000, 5000, 4000, 3000, 2000, 1200, 1000, etc. In one embodiment, the above number average molecular weight is preferably 1000 to 30000, more preferably 1000 to 15000, and even more preferably 1200 to 8000. The reasons for preference include, for example, improvement in leveling property.

[0074] Molecular weight distribution: Mw / Mn (urethane bond-containing poly(ethylenically unsaturated) compound) 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 above molecular weight distribution is preferably 1.0 to 5, more preferably 4 or less, and even more preferably 3 or less. The reason for preference is, for example, improvement in leveling property, etc.

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

[0076] The double bond equivalent (urethane bond-containing poly(ethylenically unsaturated) compound) 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 above double bond equivalent is preferably 120 g / eq to 300 g / eq.

[0077] The mass% content (urethane bond-containing poly(ethylenically unsaturated) compound / non-volatile content of the active energy ray curable composition) is, 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 above content is preferably 5 mass% to 80 mass%.

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

[0079] "The compound having three or more (ethylenically unsaturated) bonds without urethane bonds" means a compound without urethane bonds having three or more ethylenically unsaturated bonds.

[0080] Examples of the compound having three or more (ethylenically unsaturated) bonds without urethane bonds include poly(meth)acrylate without urethane bonds.

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

[0082] Examples of the compound having three or more (ethylenically unsaturated) bonds without urethane bonds include (poly)pentaerythritol poly(alkylene oxide-modified or epoxy-modified)(meth)acrylate, (poly)trimethylolpropane poly(alkylene oxide-modified or epoxy-modified)(meth)acrylate, (poly)glycerin poly(alkylene oxide-modified or epoxy-modified)(meth)acrylate, poly(alkylene oxide-modified or epoxy-modified)(meth)acrylate containing an isocyanurate structure, (poly)alkylene di(alkylene oxide-modified or epoxy-modified)(meth)acrylate, bisphenol A di(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 (in the compound having three or more (ethylenically unsaturated) bonds without urethane bonds) is, 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 above number is preferably 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 formula (A’), etc.

Chemical formula

Chemical formula

Chemical formula

[0086] Note that "may have different bases for each structural unit" means that in formula (A’), for example, when n is 2,

Chemical formula

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

[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), and the like.

[0089] Examples of pentaerythritol polyepoxy-modified (meth)acrylate include pentaerythritol diepoxy(meth)acrylate, pentaerythritol triepoxy(meth)acrylate, pentaerythritol tetraepoxy(meth)acrylate, and the like.

[0090] Examples of 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 hepta(meth)acrylate, tripentaerythritol octa(meth)acrylate, and the like.

[0091] Polypentaerythritol polyalkylene oxide-modified (meth)acrylate includes, 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), and the like.

[0092] Polypentaerythritol polyepoxy-modified (meth)acrylate includes, for example, 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, and the like.

[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') or the like. [Chemical formula] [In the formula, m represents an integer from 0 to 2. R b7’ ~R b10 ’ are each independently a hydrogen atom, [Chemical formula] and represent. R b9’ may have different bases for each structural unit. In formula (B ’ ), [Chemical formula] Two or more are included. q represents an integer from 0 to 16. R 1’ ~R 3 ’Each independently represents a hydrogen atom or an alkyl group. R 1’ The groups may be different for each unit.

[0094] Trimethylolpropane poly(meth)acrylate includes, for example, trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, etc.

[0095] Trimethylolpropane polyalkylene oxide-modified (meth)acrylate includes, for example, trimethylolpropane di(ethylene oxide-modified (meth)acrylate), trimethylolpropane tri(ethylene oxide-modified (meth)acrylate), trimethylolpropane di(propylene oxide-modified (meth)acrylate), trimethylolpropane tri(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] Polytriethylolpropane poly(meth)acrylate includes, for example, ditrimethylolpropane di(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, etc.

[0098] The polytrimethylolpropane polyalkylene oxide-modified (meth)acrylate includes, for example, ditrimethylolpropane di(ethylene oxide-modified (meth)acrylate), ditrimethylolpropane tri(ethylene oxide-modified (meth)acrylate), ditrimethylolpropane tetra(ethylene oxide-modified (meth)acrylate), ditrimethylolpropane di(propylene oxide-modified (meth)acrylate), ditrimethylolpropane tri(propylene oxide-modified (meth)acrylate), ditrimethylolpropane tetra(propylene oxide-modified (meth)acrylate), etc.

[0099] The polytrimethylolpropane polyepoxy-modified (meth)acrylate includes, for example, ditrimethylolpropane diepoxy(meth)acrylate, ditrimethylolpropane triepoxy(meth)acrylate, ditrimethylolpropane tetraepoxy(meth)acrylate, etc.

[0100] <(Poly)glycerin poly(alkylene oxide-modified or epoxy-modified)(meth)acrylate> (Poly)glycerin poly(alkylene oxide-modified or epoxy-modified)(meth)acrylate is a compound represented by formula (C’), etc. [Chemical formula] [In the formula, p represents an integer from 0 to 7. R b11’ ~R b14 ’ are each independently a hydrogen atom, [Chemical formula] and represent. R b13’ may have different bases for each structural unit. In formula (C ’ ), [Chemical formula] two or more are included. q represents an integer from 0 to 16. R 1’ ~R 3 ’ each independently represents a hydrogen atom or an alkyl group. R 1’ The groups may be different for each unit.

[0101] Examples of glycerin poly(meth)acrylate include glycerin di(meth)acrylate, glycerin tri(meth)acrylate, and the like.

[0102] Examples of glycerin polyalkylene oxide-modified (meth)acrylate include glycerin di(ethylene oxide-modified (meth)acrylate), glycerin tri(ethylene oxide-modified (meth)acrylate), glycerin di(propylene oxide-modified (meth)acrylate), glycerin tri(propylene oxide-modified (meth)acrylate), and the like.

[0103] Examples of glycerin polyepoxy-modified (meth)acrylate include glycerin diepoxy(meth)acrylate, glycerin triepoxy(meth)acrylate, and the like.

[0104] Examples of polyglycerin poly(meth)acrylate include diglycerin di(meth)acrylate, diglycerin tri(meth)acrylate, diglycerin tetra(meth)acrylate, triglycerin di(meth)acrylate, triglycerin tri(meth)acrylate, triglycerin tetra(meth)acrylate, triglycerin penta(meth)acrylate, and the like.

[0105] Poly-glycerin poly-alkylene oxide modified (meth)acrylate includes, for example, diglycerin di(ethylene oxide modified (meth)acrylate), diglycerin tri(ethylene oxide modified (meth)acrylate), diglycerin tetra(ethylene oxide modified (meth)acrylate), triglycerin di(ethylene oxide modified (meth)acrylate), triglycerin tri(ethylene oxide modified (meth)acrylate), triglycerin tetra(ethylene oxide modified (meth)acrylate), triglycerin penta(ethylene oxide modified (meth)acrylate), diglycerin di(propylene oxide modified (meth)acrylate), diglycerin tri(propylene oxide modified (meth)acrylate), diglycerin tetra(propylene oxide modified (meth)acrylate), triglycerin di(propylene oxide modified (meth)acrylate), triglycerin tri(propylene oxide modified (meth)acrylate), triglycerin tetra(propylene oxide modified (meth)acrylate), triglycerin penta(propylene oxide modified (meth)acrylate), etc.

[0106] Poly-glycerin poly-epoxy modified (meth)acrylate includes, for example, diglycerin diepoxy(meth)acrylate, diglycerin triepoxy(meth)acrylate, diglycerin tetraepoxy(meth)acrylate, triglycerin diepoxy(meth)acrylate, triglycerin triepoxy(meth)acrylate, triglycerin tetraepoxy(meth)acrylate, triglycerin pentaepoxy(meth)acrylate, etc.

[0107] <Poly(isocyanurate structure-containing poly(alkylene oxide modified or epoxy modified)(meth)acrylate)> Poly(isocyanurate structure-containing poly(alkylene oxide modified or epoxy modified)(meth)acrylate) is a compound represented by formula (D’), etc. [Chemical formula] [In the formula, Rb15’ ~R b17 ’ each independently represents a hydrogen atom,

Chem.

Chem.

[0108] Examples of the poly(meth)acrylate containing an isocyanurate structure include di(meth)acrylate isocyanurate, tri(meth)acrylate isocyanurate, and the like.

[0109] Examples of the polyalkylene oxide-modified (meth)acrylate containing an isocyanurate structure include di(ethylene oxide-modified (meth)acrylate) isocyanurate, tri(ethylene oxide-modified (meth)acrylate) isocyanurate, and the like.

[0110] Examples of the polyepoxy-modified (meth)acrylate containing an isocyanurate structure include diepoxy-modified (meth)acrylate isocyanurate, triepoxy-modified (meth)acrylate isocyanurate, and the like.

[0111] The hydroxyl value (for compounds with three or more (ethylenically unsaturated) groups not containing urethane bonds) is, for example, 300 mg KOH / g, 275 mg KOH / g, 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, 90 mg KOH / g, 80 mg KOH / g, 70 mg KOH / g, 60 mg KOH / g, 50 mg KOH / g, 40 mg KOH / g, 30 mg KOH / g, 20 mg KOH / g, 10 mg KOH / g, 0 mg KOH / g, etc. In one embodiment, the above hydroxyl value is preferably from 0 mg KOH / g to 300 mg KOH / g. The preferred reasons include, for example, improvement in antiglare properties, etc.

[0112] The mass% content (compounds with three or more (ethylenically unsaturated) groups not containing urethane bonds / non-volatile content of the active energy ray curable composition) is, 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 above content is preferably from 0 mass% to 90 mass%, more preferably from 0 mass% to 70 mass%.

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

[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, and the like.

[0117] In one embodiment, the particulate state preferably includes a powder or a solvent-dispersed sol.

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

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

[0120] ((Meth)acryloyl group-containing inorganic particles) In one embodiment, the inorganic particles preferably include (meth)acryloyl group-containing inorganic particles.

[0121] (Meth)acryloyl group-containing inorganic particles are reaction products of inorganic particles and (meth)acryloyl group-containing compounds.

[0122] (((Meth)acryloyl group-containing compound)) (Meth)acryloyl group-containing compounds can be used alone or in combination of two or more.

[0123] 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.)

[0124] -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 can be used alone or in combination of two or more. In one embodiment, the above groups preferably include -O-C(=O)-NH-, -O-C(=S)-NH-, -S-C(=O)-NH-. The preferred reasons include, for example, improved thermal stability, etc.

[0125] The above group [-X-C(=Y)-NH-] is considered to generate an appropriate cohesive force by hydrogen bonding between molecules, and when formed into a cured product, it imparts properties such as excellent mechanical strength, adhesion to the substrate, and heat resistance. It should be noted that the above is only one theory, and the present invention is not intended to be restricted by the above theory.

[0126] The above (meth)acryloyl group-containing compound preferably includes a silanol group-containing compound and a silanol group-forming compound.

[0127] 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 a compound containing an alkoxy group or an aryloxy group.

[0128] The silanol group or the silanol group-forming site of the silanol group-forming compound is a structural unit that binds to the particles by a condensation reaction or a condensation reaction following hydrolysis.

[0129] In one embodiment, the (meth)acryloyl group-containing compound preferably includes a compound represented by the following formula S.

Chemical formula

[0130] In formula S, (R s1 O) s’ R s2 3-s’ Si- includes, for example, a trimethoxysilyl group, a triethoxysilyl group, a triphenoxysilyl group, a methyldimethoxysilyl group, a dimethylmethoxysilyl group, etc. In one embodiment, (R s1 O) s’ R s2 3-s’ Si- preferably includes a trimethoxysilyl group and a triethoxysilyl group.

[0131] In formula S, R s4 includes, for example, an alkylene group, an arylene group, etc. R s4 optionally may contain elements other than carbon atoms and hydrogen atoms. R s4 optionally may 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 (R s4 ) is preferably from 14 to 10,000, more preferably from 76 to 500.

[0133] In formula S, R s5 includes, for example, an alkylene group, an arylene group, etc. R s5 optionally may contain elements other than carbon atoms and hydrogen atoms. R s5 optionally may 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 is, for example, the following groups and the like.

Chemical formula

[0135] In formula S, s'' is preferably 1 to 20, more preferably 1 to 10, and even more 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 JP-A-9-100111 and the like. Examples of the above synthesis method include the following methods. (A) Method: Addition reaction of mercaptoalkoxysilane, polyisocyanate, and active hydrogen group-containing (meth)acrylate (B) Method: Reaction of a compound having an alkoxysilyl group and an isocyanate group with an active hydrogen-containing (meth)acrylate (C) Method: Addition reaction of a compound having a (meth)acryloyl group and an isocyanate group with mercaptoalkoxysilane or aminosilane

[0137] In one embodiment, the method for synthesizing the (meth)acryloyl group-containing compound represented by formula S preferably includes the above (A) method. Examples of the above (A) method include the following methods. (A1) Method: First, react mercaptoalkoxysilane and polyisocyanate to form an intermediate containing an alkoxysilyl group, [-S-C(=O)NH-] group, and isocyanate group, and then react the intermediate with a hydroxyl group-containing (poly)(meth)acrylate to form a [-O-C(=O)NH-] bond. (A2) Method; First, a step of forming an intermediate containing a (meth)acryloyl group, [-O-C(=O)NH-] group, and isocyanate group by reacting a polyisocyanate with a hydroxyl group-containing (poly)(meth)acrylate, and a step of reacting the intermediate with a mercaptoalkoxysilane to form a [-S-C(=O)-NH-] bond In one embodiment, the (A1) method is preferred in that there is no reduction in polymerizable unsaturated groups by Michael addition reaction.

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

[0139] Examples of the mercaptoalkoxysilane include mercaptopropyltrimethoxysilane, mercaptopropyltriethoxysilane, mercaptopropylmethyldiethoxysilane, mercaptopropyldimethoxymethylsilane, mercaptopropylmethoxydimethylsilane, mercaptopropyltriphenoxysilane, mercaptopropyltributoxysilane, and the like.

[0140] In one embodiment, the mercaptoalkoxysilane preferably includes 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 and the like.

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

[0143] Examples of the hydroxyl group-containing (poly)(meth)acrylate include hydroxyl group-containing (meth)acrylate, hydroxyl group-containing poly(meth)acrylate, and the like.

[0144] Hydroxyl group-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, and the like.

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

[0146] In one embodiment, the hydroxyl group-containing poly(meth)acrylate preferably includes trimethylolpropane di(meth)acrylate, trimethylolethane di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate.

[0147] In one embodiment, the hydroxyl group-containing (poly)(meth)acrylate preferably includes 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 compounds represented by the following formula.

Chemical formula

[0150] The compound represented by formula U1 includes, for example, 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, (meth)acryloxypropyl triphenoxysilane, and the like.

[0151] The method for producing (meth)acryloyl group-containing inorganic particles includes, for example, a step of hydrolyzing alkoxysilane to obtain an alkoxysilane hydrolyzate, a step of mixing the alkoxysilane hydrolyzate with powder silica particles or a solvent dispersion sol of silica particles and performing heating and stirring operations, a method of performing hydrolysis of alkoxysilane in the presence of particles, and the like. In one embodiment, the production method ((meth)acryloyl group-containing inorganic particles) preferably includes a method of performing hydrolysis of alkoxysilane in the presence of particles.

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

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

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

[0155] Desiccants include, for example, inorganic desiccants, organic desiccants, and the like.

[0156] Inorganic desiccants include, for example, zeolite, anhydrous silica, anhydrous alumina, and the like.

[0157] Organic desiccants include, for example, methyl orthoformate, ethyl orthoformate, tetraethoxymethane, tetrabutoxymethane, and the like.

[0158] In one embodiment, the desiccant preferably includes an organic desiccant, 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-. (In the formula, X represents NH, O, or S. Y represents O or S.)

[0161] (Organic particles) Organic particles include, for example, acrylic particles, styrene-acrylic particles, polystyrene particles, polyacrylonitrile particles, melamine particles, polyethylene particles, benzoguanamine particles, and the like.

[0162] In one embodiment, the organic particles preferably include acrylic particles and styrene-acrylic particles, more preferably crosslinked acrylic particles and crosslinked styrene-acrylic particles, and even more preferably crosslinked methyl methacrylate particles and crosslinked methyl methacrylate-styrene particles.

[0163] "A particles" means particles containing A resin as a raw material.

[0164] Commercially available products (acrylic particles) include, for example, Epotar MA1004, MA1006 (manufactured by Nippon Shokubai Co., Ltd.), Toughtic FH-S005 (manufactured by Nippon Exlan 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.), and the like.

[0165] Commercially available products (styrene-acrylic particles) include, for example, Epotar MA2003 (manufactured by Nippon Shokubai Co., Ltd.), Tech Polymer MSX, SMX (manufactured by Sekisui Chemical Co., Ltd.), and the like.

[0166] Commercially available products (polystyrene particles) include, for example, Tech Polymer SBX-4 (manufactured by Sekisui Chemical Co., Ltd.), Chemisnow SX-130H, SX-350H, SX-500H (manufactured by Soken Chemical & Engineering Co., Ltd.), and the like.

[0167] Commercially available products (polyacrylonitrile particles) include, for example, Toughtic ASF (manufactured by Nippon Exlan Co., Ltd.), and the like.

[0168] Commercially available products (melamine particles) include, for example, Epotar SS, Epotar S, Epotar FS, Epotar S6, Epotar 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.), Chemipar W500 (manufactured by Mitsui Chemicals, Inc.), and the like.

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

[0171] Manufacturing methods (for 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. (of particles)) The particle size (of 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 above particle size is preferably 5 nm to 100 nm. The reasons for preference include, for example, hardness, flexibility, and the like.

[0173] The particle size (of 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 above particle size is preferably 0.5 μm to 10 μm. The reasons for preference include, for example, improvement of antiglare properties.

[0174] "Particle size" means the volume-average particle size. "Volume-average particle size" means the particle size at which the volume-based particle size distribution is 50% when integrated from the small particle size side for the volume-based particle size distribution measured using the dynamic light scattering method.

[0175] The volume-based particle size distribution can be measured by the following procedure. <Inorganic fine particles> (1) Preparation of the measurement solution Propylene glycol monomethyl ether (hereinafter, PGME; for example, manufactured by Nippon Emulsifier Co., Ltd.) is added with a measurement sample (particles) so that the measurement sample concentration becomes 1% by mass to prepare a solution. (2) Measurement of the volume-based particle size distribution Measuring instrument: Dynamic light scattering type particle size distribution measuring device "LB-550" (manufactured by Horiba, Ltd.) Number of measurements: 5 Measured temperature: 25 ± 0.5 °C Measuring time: 60 seconds Upper measurement limit: 6000 nm Lower measurement limit: 1 nm Measurement solvent: Refractive index of PGME: 1.404 <Organic microparticles> (1) Measurement of volume-based particle size distribution Measuring instrument: "Microtrac MT3000II" (Microtrac BEL) Number of measurements: 2 Measured temperature: Room temperature Measuring time: 30 seconds Upper measurement limit: 1400 μm Lower measurement limit: 0.2 μm Measurement solvent: Refractive index of PGME: 1.404 Note that the refractive index of the measurement sample (particles) can be referred to literature values (such as "A GUIDE FOR ENTERING MICROTRAC ”RUN INFORMATION”(F3)DATA", created by Leeds&Northrup).

[0176] The refractive index of (inorganic particles) includes, for example, 2.5, 2.3, 2.1, 2.0, 1.9, 1.7, 1.5, 1.3, 1.2, etc. In one embodiment, the above refractive index is preferably 1.2 to 2.5.

[0177] The refractive index of (organic particles) includes, for example, 1.65, 1.63, 1.61, 1.60, 1.59, 1.57, 1.55, 1.53, 1.51, 1.50, 1.49, etc. In one embodiment, the above refractive index is preferably 1.49 to 1.65.

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

[0179] The particle shape includes, for example, spherical, hollow, solid, porous, rod-shaped, plate-shaped, fibrous, irregular shape, etc.

[0180] Examples of the particles include hydrophilic particles, hydrophobic particles, and the like.

[0181] The mass% content (particles / non-volatile content of the active energy ray curable composition) can be, 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%, and the like. In one embodiment, the above content is preferably 0 mass% to 85 mass%, more preferably 0 mass% to 40 mass%.

[0182] The mass% content (inorganic particles / non-volatile content of the active energy ray curable composition) can be, 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%, and the like. In one embodiment, the above content is preferably 0 mass% to 85 mass%, more preferably 0 mass% to 40 mass%.

[0183] The mass% content (organic particles / non-volatile content of the active energy ray curable composition) can be, for example, 30 mass%, 25 mass%, 20 mass%, 15 mass%, 10 mass%, 5 mass%, 0 mass%, and the like. In one embodiment, the above content is preferably 0 mass% to 30 mass%, more preferably 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] Non-polar monomers include, for example, unsubstituted alkyl esters of (meth)acrylic acid, alkenyl aryl compounds, and the like.

[0187] Unsubstituted alkyl esters of (meth)acrylic acid include, for example, unsubstituted linear alkyl esters of (meth)acrylic acid, unsubstituted branched alkyl esters of (meth)acrylic acid, unsubstituted alicyclic alkyl esters of (meth)acrylic acid, and the like.

[0188] Unsubstituted linear alkyl esters of (meth)acrylic acid include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, n-amyl (meth)acrylate, n-hexyl (meth)acrylate, n-octyl (meth)acrylate, n-nonyl (meth)acrylate, n-decyl (meth)acrylate, n-undecyl (meth)acrylate, lauryl (meth)acrylate, tridecyl (meth)acrylate, myristyl (meth)acrylate, pentadecyl (meth)acrylate, palmityl (meth)acrylate, heptadecyl (meth)acrylate, stearyl (meth)acrylate, and the like.

[0189] Unsubstituted branched alkyl esters of (meth)acrylic acid include, for example, i-propyl (meth)acrylate, i-butyl (meth)acrylate, i-amyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and the like.

[0190] Unsubstituted alicyclic alkyl esters of (meth)acrylic acid include, for example, cyclohexyl (meth)acrylate, and the like.

[0191] Alkenyl aryl compounds include, for example, styrene, α-methylstyrene, p-methylstyrene, vinyltoluene, divinylbenzene, and the like.

[0192] The mass% content (non-polar monomer unit / polymer) is, for example, 99% by mass, 95% by mass, 90% by mass, 85% by mass, 80% by mass, 75% by mass, 70% by mass, 65% by mass, 60% by mass, 55% by mass, 50% by mass, 45% by mass, 40% by mass, 35% by mass, 30% by mass, 25% by mass, 20% by mass, 15% by mass, 10% by mass, 5% by mass, 2% by mass, 1% by mass, 0% by mass, etc. In one embodiment, the above content is preferably 0% by mass to 99% by mass, more preferably 60% by mass to 99% by mass, and still more preferably 65% by mass to 95% by mass.

[0193] The molar% content (non-polar monomer unit / polymer) is, 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 above content is preferably 0 mol% to 99 mol%, more preferably 50 mol% to 99 mol%, and still more preferably 65 mol% to 96 mol%. Preferred reasons include, for example, improved leveling property, improved compatibility, etc.

[0194] (Hydroxyl group-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.

[0195] Examples of the hydroxyl group-containing monomer include hydroxyl group-containing (meth)acrylate, hydroxyl group-containing vinyl ether, etc.

[0196] Examples of the hydroxyl group-containing (meth)acrylate include hydroxyl group-containing linear (meth)acrylate, hydroxyl group-containing branched (meth)acrylate, etc.

[0197] Examples of the hydroxyl group-containing linear (meth)acrylic acid ester include 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and the like.

[0198] Examples of the hydroxyl group-containing branched (meth)acrylic acid ester 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, 1,1-dimethyl-2-hydroxyethyl (meth)acrylate, and the like.

[0199] Examples of the hydroxyl group-containing vinyl ether include hydroxyalkyl vinyl ether, polyalkylene glycol monovinyl ether, and the like.

[0200] Examples of the hydroxyalkyl vinyl ether include hydroxy linear alkyl vinyl ether, hydroxy branched alkyl vinyl ether, hydroxy cycloalkyl vinyl ether, and the like.

[0201] Examples of the polyalkylene glycol monovinyl ether include polymethylene glycol monovinyl ether, polyethylene glycol monovinyl ether, polypropylene glycol monovinyl ether, and the like.

[0202] The mass percentage content (hydroxyl group-containing monomer unit / polymer) includes, for example, 40% by mass, 35% by mass, 30% by mass, 25% by mass, 20% by mass, 15% by mass, 10% by mass, 5% by mass, 2% by mass, 1% by mass, 0% by mass, and the like. In one embodiment, the above content is preferably 0% by mass to 40% by mass, more preferably 1% by mass to 40% by mass, and even more preferably 5% to 30% by 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%, and the like. In one embodiment, the above content is preferably 0 mol% to 40 mol%, and more preferably 4 mol% to 35 mol%. The reasons for preference include, for example, improvement in leveling property, improvement in compatibility, and the like.

[0204] (Unsaturated carboxylic acid (salt) unit) In one embodiment, the above polymer may optionally contain an unsaturated carboxylic acid (salt) unit. 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, and the like.

[0206] Examples of the unsaturated carboxylic acid salt include unsaturated carboxylic acid inorganic salts, unsaturated carboxylic acid organic salts, and the like.

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

[0208] Examples of the unsaturated carboxylic acid organic salt include unsaturated carboxylic acid amines and the like.

[0209] The mass% content (unsaturated carboxylic acid (salt) unit / polymer) is, 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 above content is preferably 0 mass% to 30 mass%.

[0210] The molar% content (unsaturated carboxylic acid (salt) unit / polymer) is, 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 above content is preferably 0 mol% to 38 mol%.

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

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

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

[0214] The mass% content (other constitutional units / polymer) is, for example, 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] The mass% content (other constitutional units / any one of the constitutional units of non-polar monomer units, hydroxyl group-containing monomer units, and unsaturated carboxylic acid (salt) units) is, for example, 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] The molar% content (other constituent units / polymer) is, for example, less than 10 mol%, less than 5 mol%, less than 2 mol%, less than 1 mol%, less than 0.1 mol%, 0 mol%, etc.

[0217] The molar% content (other constituent units / any one of the constituent units of nonpolar monomer units, hydroxyl group-containing monomer units, unsaturated carboxylic acid (salt) units) is, for example, less than 10 mol%, less than 5 mol%, less than 2 mol%, less than 1 mol%, less than 0.1 mol%, 0 mol%, etc.

[0218] <Physical properties, etc. (polymer)> The glass transition temperature (polymer) is, 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 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 charged amount of the monomer used in the production of the polymer can be accurately grasped and the polymerization rate is high, the glass transition temperature is calculated from Fox's equation. Fox's equation: 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 (K) of the homopolymer of monomer N

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

[0222] The hydroxyl value is measured by a method conforming to JIS K0070 (neutralization titration method).

[0223] When the charged 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 = [(mass of hydroxyl group-containing monomer charged per 1 g of total charged monomers × number of hydroxyl groups per molecule of hydroxyl group-containing monomer) / molecular weight of hydroxyl group-containing monomer] × 56.11 (molecular weight of KOH) × 1000

[0224] The acid value (polymer) can be, for example, 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 above acid value is preferably 4 mg KOH / g to 250 mg KOH / g.

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

[0226] (Meth)acrylic equivalent can be, for example, 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 above (meth)acrylic equivalent is preferably less than 150 g / eq, more preferably less than 100 g / eq, and even more preferably 0 g / eq. The preferred reasons include, for example, reduction of curl (bending) of the cured product, and compatibility between anti-glare property and mechanical properties.

[0227] “(Meth)acrylic equivalent” means the calculated value (g / eq) of the mass per mole of (meth)acryloyl group.

[0228] Weight-average molecular weight: Mw (polymer) is, for example, 400000, 300000, 290000, 285000, 284000, 280000, 250000, 200000, 175000, 150000, 140000, 126000, 125000, 120000, 110000, 100000, 90000, 88000, 80000, 70000, 65000, 60000, 50000, 40000, 37500, 35000, 30000, 28000, 25000, etc. In one embodiment, the above weight-average molecular weight is preferably 25000 to 400000, more preferably 37500 to 150000, and even more preferably 50000 to 100000. The reasons for preference include, for example, improvement in leveling property, etc.

[0229] Number-average molecular weight: Mn (polymer) is, for example, 100000, 80000, 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 above number-average molecular weight is preferably 8500 to 100000, more preferably 14000 to 35000, and even more preferably 15000 to 30000. The reasons for preference include, for example, improvement in leveling property, etc.

[0230] Molecular weight distribution: Mw / Mn (polymer) is, for example, 20, 19, 17, 15, 13, 11, 10, 9, 7, 5, 4.5, 4.2, 4, 3.5, 3, 2.5, 2.3, 2.1, etc. In one embodiment, the above molecular weight distribution is preferably 2.1 to 20, more preferably 5 or less, and even more preferably 2.5 to 4.2. The reasons for preference include, for example, improvement in leveling property, etc.

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

[0232] (Manufacturing method (polymer)) The manufacturing method (polymer) includes, for example, 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, and the like.

[0234] Examples of the inorganic peroxide include hydrogen peroxide, ammonium persulfate, potassium persulfate, and the like.

[0235] Examples of the organic peroxide include benzoyl peroxide, dicumyl peroxide, lauryl peroxide, and the like.

[0236] Examples of the azo compound include 2,2'-azobisisobutyronitrile, dimethyl-2,2'-azobisisobutyrate, and the like.

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

[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] Chain transfer agents include, for example, lauryl mercaptan, dodecyl mercaptan, 2-mercaptobenzothiazole, bromotrichloromethane, α-methylstyrene dimer, and the like.

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

[0241] The content in mass% (polymer / non-volatile content 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, and the like. In one embodiment, the above content is preferably 0% by mass to 20% by mass.

[0242] In one embodiment, the content in parts by mass [polymer / (compound having three or more (ethylenically unsaturated) groups without urethane bond and urethane bond-containing poly(ethylenically unsaturated) compound)] is preferably less than 50 parts by mass, more preferably 15 parts by mass or less. The preferred reasons include, for example, improvement of scratch resistance, improvement of pencil hardness, and the like. <Photoinitiator> In one embodiment, the active energy ray curable composition may optionally contain a photoinitiator. The photoinitiator can be used alone or in combination of two or more.

[0243] Photoinitiators include, for example, α-hydroxy dimethyl acetophenone group-containing photoinitiators, α-hydroxy cycloalkyl phenones, α-amino alkyl phenones, benzyl dimethyl ketal, unsubstituted or substituted alkyl phenones, unsubstituted or substituted benzyls, unsubstituted or substituted benzophenones, acylphosphine oxides, substituted thioxanthones, oxime esters, and the like.

[0244] Examples of the α-hydroxy dimethyl acetophenone group-containing photoinitiator include 2-hydroxy-2-methyl-1-phenylpropanone, 1-[4-(2-hydroxyethoxyl)-phenyl]-2-hydroxy-methylpropanone, 2-hydroxy-1-(4-(4-(2-hydroxy-2-methylpropionyl)benzyl)phenyl)-2-methylpropane-1-one, and the like.

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

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

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

[0248] 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'-morpholinobutyrophenone, 2-methyl-4'-(methylthio)-2-morpholinopropiophenone, 2-isonitroso propiophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, and the like.

[0249] Examples of the unsubstituted or substituted benzyl include benzyl, p-anisyl, and the like.

[0250] Non-replaced or replaced benzophenones include, for example, 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] Acylphosphine oxides include, for example, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, and the like.

[0252] Replaced thioxanthones include, for example, 2-chlorothioxanthone, 2-isopropylthioxanthone, 2,4-diethylthioxanthone, and the like.

[0253] Oxime esters include, for example, 1,2-octanedione, 1-[4-(phenylthio)-, 2-(O-benzoyloxime)] (i.e., 2-((benzoyloxy)imino)-1-(4-(phenylthio)phenyl)octan-1-one); ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acet yloxime) (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 necessary.

[0255] The mass% content (photoinitiator / non-volatile content 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 above content is preferably 0 mass% to 10 mass%, and more preferably 1 mass% to 6 mass%.

[0256] <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.

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

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

[0259] Examples of the hindered phenol include monohindered phenol.

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

[0261] Examples of the monohindered phenol 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 monohindered phenol, and still more preferably 2,6-di-tert-butyl-p-cresol. The reasons for preference include, for example, improvement of paint stability.

[0263] The mass% content (polymerization inhibitor / non-volatile content 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 above 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 may 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, haloalkane solvents, amide solvents, and the like.

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

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

[0268] Examples of the alcohol solvent include methanol, ethanol, n-propanol, isopropanol, n-butanol, i-butanol, t-butanol, and the like.

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

[0270] Glycol ether solvents include, for example, 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, ethylene glycol mono-t-butyl ether, and the like.

[0271] Ester solvents include, for example, ethyl acetate, butyl acetate, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, and the like.

[0272] Petroleum solvents include, for example, Solvesso #100 (manufactured by Exxon), Solvesso #150 (manufactured by Exxon), and the like.

[0273] Haloalkane solvents include, for example, chloroform and the like.

[0274] Amide solvents include, for example, dimethylformamide and the like.

[0275] In one embodiment, the organic solvent is preferably an alcohol solvent or a glycol ether solvent, more preferably isopropyl alcohol, n-butanol, isobutanol, or propylene glycol monomethyl ether, still more preferably a combination of isopropyl alcohol and propylene glycol monomethyl ether, or a combination of n-butanol and propylene glycol monomethyl ether, and particularly preferably a combination of isopropyl alcohol and propylene glycol monomethyl ether. The preferred reasons include, for example, improved leveling properties.

[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 above content is preferably 0 mass% to 99 mass%.

[0277] <Additive> The active energy ray curable composition may optionally contain an agent (additive) that does not fall under any of the above.

[0278] Examples of the additive include an ultraviolet absorber, an antifoaming agent, a surface conditioner, an antifouling agent, a pigment, 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 / urethane bond-free di (ethylenically unsaturated) compound), the parts by mass content (additive / urethane bond-containing poly (ethylenically unsaturated) compound), and the parts by mass content (additive / urethane bond-free tri or more (ethylenically unsaturated) compounds) 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] By dispersing and mixing the above agent, an active energy ray curable composition can be produced.

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

[0283] Uses (active energy ray curable composition) include, for example, coating agents, hard coating agents, clear coating agents, clear hard coating agents, antiglare coating agents, antiglare 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, antiglare coating agents for acrylic substrates, antiglare hard coating agents for acrylic substrates, etc.

[0284] Specific active energy ray curable composition compositions include, for example, the following compositions, etc. The numbers in the table represent parts by mass. Also, 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] The present disclosure relates to a cured product of the above active energy ray curable composition.

[0287] The curing conditions include, for example, the following conditions.

[0288] [Laminate] The present disclosure relates to a laminate including the above cured product.

[0289] The manufacturing method (laminate) includes, for example, a method including 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 a substrate Active energy ray curing step: a step of irradiating active energy rays to form a cured product layer of the active energy ray curable composition

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

[0291] In one embodiment, the thickness (substrate) is preferably 10 μm to 2000 μm.

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

[0293] (Coating process) Examples of the coating method include bar coater coating, wire bar coating, Mayer bar coating, air knife coating, gravure coating, reverse gravure coating, flow coater coating, offset printing, flexographic printing, screen printing method, and the like.

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

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

[0296] When using a high-pressure mercury lamp, the curing conditions preferably include the following conditions and the like. Lamp output: 25 W / cm to 160 W / cm UV illuminance: 10 mW / cm 2 ~800 mW / cm 2 Integrated light quantity: 25 mJ / cm 2 ~2000 mJ / cm 2 Conveyor speed: 1 m / min to 50 m / min

[0297] When using an electron beam, the curing conditions preferably include the following conditions and the like. Acceleration voltage: 10 kV to 300 kV Conveyor speed: 5 m / min to 50 m / min

Examples

[0298] Hereinafter, the present invention will be specifically described through 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 limited only by the scope of the claims. Unless otherwise specifically described below, numerical values such as parts and % are based on mass.

[0299] Production Example 1-1: Polymer Into a four-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, thermometer, and dropping funnel, 0.5 part of 2,2'-azobis(2-methylbutyronitrile) as a polymerization initiator and 186 parts of propylene glycol monomethyl ether (PGME) were added. While dropping the monomers described in the following table into the reaction vessel, 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 content concentration: 30%).

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

[0301] [Table 1] MMA: Methyl methacrylate HEMA: 2-Hydroxyethyl methacrylate HEA: 2-Hydroxyethyl acrylate Glass transition temperature: Calculated value (Fox's equation) Hydroxyl value: Calculated value (formula described in the specification)

[0302] Production Example 1-3 Into a four-necked flask equipped with a stirrer, thermometer, reflux cooler, and 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 charged and stirred. After heating to 85 °C under a nitrogen stream, the reaction was carried out for 10 hours. After the reaction was completed, it was cooled to 60 °C, and 50 parts of acrylic acid, 0.1 part of triphenylphosphine, and 0.05 part of methoquinone were charged. The nitrogen inlet was replaced with an air bubbling device, and while stirring and bubbling air into the reaction solution, 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).

[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 Corporation Temperature increase 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: HLC-8420, manufactured by Tosoh Corporation · Column: Product name "TSKgel SuperHZM-M" (manufactured by Tosoh Corporation) × 3 columns · Eluent: Tetrahydrofuran · Column temperature: 40 °C · Calibration curve: Monodisperse polystyrene · Detector: RI · Concentration of polymer: 1 mass% · Measuring method: Measurement after filtration through a filter.

[0305] Production Example 2-1: Urethane bond-containing poly(ethylenically unsaturated) compound Into a reaction vessel equipped with a stirrer and a condenser, the raw materials described in the following table and 0.05 part of tin octylate were charged, and then the temperature inside 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 urethane bond-containing poly(ethylenically unsaturated) compound.

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

[0307]

Table 2

[0308] Example 1: Active energy ray curable composition As non-volatile components, the substances listed in the following table were mixed and then diluted with PGME to obtain an active energy ray curable composition (non-volatile content: 30%).

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

[0310] [Table 3] VEEA: manufactured by Nippon Shokubai Co., Ltd. V#195: Biscoat #195, manufactured by Osaka Organic Chemical Industry Co., Ltd. V#230: Biscoat #230, manufactured by Osaka Organic Chemical Industry Co., Ltd. FA-222A: Funacryl-222A, manufactured by Resona Co., Ltd. Light Ester EG: manufactured by Kyoeisha Chemical Co., Ltd. V#260: Biscoat #260, manufactured by Osaka Organic Chemical Industry Co., Ltd. V#295: Biscoat #295, manufactured by Osaka Organic Chemical Industry Co., Ltd. V#300: Biscoat #300, manufactured by Osaka Organic Chemical Industry Co., Ltd. V#150: Biscoat #150, manufactured by Osaka Organic Chemical Industry Co., Ltd. V#160: Biscoat #160, manufactured by Osaka Organic Chemical Industry Co., Ltd. Omnirad 2959: 1-[4-(2-hydroxyethoxyl)-phenyl]-2-hydroxy-methylpropanone, manufactured by IGM Resins

[0311] (Laminate) The active energy ray curable composition was applied to a substrate under the following conditions. Next, the coated article was dried under the following conditions. Then, the dried article was cured under the following conditions to obtain a laminate. · Coating conditions Base material: Acrylic film (40 μm), manufactured by Okura Industries Co., Ltd. Coating method: Bar coater, model number "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 Integrated irradiation dose: 190 mJ / cm 2 Under a nitrogen atmosphere (oxygen concentration 400 ppm or less)

[0312] (Adhesion) A 100-grid crosscut test was conducted using a Nichiban Co., Ltd. Elpack LP-24 (24 mm width) tape (tested 3 times at the same location). 5B: No peeling 4B: Edge chipping occurs or peeling occurs in less than 5% of the test area 3B: Peeling occurs in 5% or more but less than 15% of the test area 2B: Peeling occurs in 15% or more but less than 35% of the test area 1B: Peeling occurs in 35% or more but less than 65% of the test area 0B: Peeling occurs in 65% or more of the test area

Claims

Claim 1 An active energy ray-curable composition, wherein the active energy ray-curable composition contains a urethane bond-free di(ethylenically unsaturated) compound and a urethane bond-containing poly(ethylenically unsaturated) compound, and the molecular weight of the urethane bond-free di(ethylenically unsaturated) compound is 260 or less. Active energy ray-curable composition. Claim 2 The active energy ray-curable composition according to claim 1, containing particles. Claim 3 A cured product of the active energy ray-curable composition according to claim 1 or 2. Claim 4 A laminate containing the cured product according to claim 3.

Images