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 compound A and a compound B, the double bond equivalent weight of the compound A being 200 g / eq or more, the double bond equivalent weight of the compound B being 28 g / eq or more but less than 200 g / eq, and the double bond equivalent weight of the entire active energy ray-curable composition being less than 365 g / eq, the amount of dissolved oxygen is more than 10 vol% with respect to 100 vol% of dissolved gas, and the iron atom content is 400 ppb or less and the copper atom content is 300 ppb or less with respect to the entire active energy ray-curable composition.

Description

Technical Field

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

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

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

[0004] The problem to be solved by the present invention is to provide an active energy ray-curable composition which can produce a cured product having excellent curability and contamination resistance and excellent stability. [Technical means to solve technical problems]

[0005] According to the present disclosure, the following items are provided. (Item 1) An active energy ray-curable composition, The active energy ray-curable composition comprises: a compound A and a compound B, The double bond equivalent of the compound A is greater than 200 g / eq, and the double bond equivalent of the compound B is greater than 28 g / eq and less than 200 g / eq, The active energy ray-curable composition has a double bond equivalent of less than 365 g / eq. The amount of dissolved oxygen relative to 100% by volume of the dissolved gas is greater than 10% by volume. With respect to the entire active energy ray-curable composition, The iron atom content is 400 ppb or less, and the copper atom content is 300 ppb or less. (Item 2) A cured product of the active energy ray-curable composition according to the above item. (Item 3) A laminate comprising the cured product according to the above item.

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

[0007] The active energy ray-curable composition of the present invention exhibits excellent stability. In addition, the cured product of the present invention exhibits excellent curability and stain resistance. DETAILED DESCRIPTION

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

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

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

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

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

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

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

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

[0016] Examples of the branched alkyl group include isopropyl, diethylpentyl, trimethylbutyl, trimethylpentyl, and trimethylhexyl.

[0017] Examples of the cycloalkyl group include a monocyclic cycloalkyl group, a bridged ring cycloalkyl group, a condensed ring cycloalkyl group, etc. Furthermore, a group in which at least one hydrogen atom of a cycloalkyl group is substituted by an alkyl group is also regarded as a cycloalkyl group.

[0018] "Single ring" refers to a ring structure formed by covalent bonds of carbon without a bridging structure inside. "Fused ring" refers to a ring structure in which two or more single rings share two atoms (i.e., only one side of each ring is shared (fused) with each other). "Bridged ring" refers to a ring structure in which two or more single rings share three or more atoms.

[0019] Examples of the monocyclic cycloalkyl group include cyclopentyl, cyclohexyl, cycloheptyl, cyclodecyl, and 3,5,5-trimethylcyclohexyl.

[0020] Examples of the bridged cycloalkyl group include tricyclodecanyl, adamantyl, and norbornyl.

[0021] In addition, the alkyl group also includes a group in which a linear alkyl group, a branched alkyl group, and a cycloalkyl group are combined. Examples of such a group in which a linear alkyl group, a branched alkyl group, and a cycloalkyl group are combined include a cycloalkylalkyl group and the like.

[0022] The cycloalkylalkyl group is represented by the following formula. R calkyl -R alkyl - (Where R calkyl represents a cycloalkyl group. alkyl represents an alkyl group. )

[0023] Examples of the alkylene group include a linear alkylene group, a branched alkylene group, and a cycloalkylene group.

[0024] Examples of the linear alkylene group include methylene, ethylene, n-propylene, n-butylene, n-pentylene, n-hexylene, n-heptylene, n-octylene, n-nonylene, and n-decylene.

[0025] Examples of the branched alkylene group include diethylpentylene, trimethylbutylene, trimethylpentylene, and trimethylhexylene.

[0026] Examples of the cycloalkylene group include monocyclic cycloalkylene groups, bridged cycloalkylene groups, condensed cycloalkylene groups, etc. Furthermore, one or more hydrogen atoms of the cycloalkylene group may be substituted with a linear or branched alkyl group.

[0027] Examples of the monocyclic cycloalkylene group include cyclopentylene, cyclohexylene, cycloheptylene, cyclodecylene, and 3,5,5-trimethylcyclohexylene.

[0028] Examples of the bridged ring cycloalkylene group include tricyclodecanylene, adamantylene, and norbornylene.

[0029] Examples of the fused ring cycloalkylene group include bicyclodecanylene and the like.

[0030] In addition, the alkylene group also includes a group in which a linear alkylene group, a branched alkylene group, and a cycloalkylene group are combined. Examples of such a group include a cycloalkylene alkylene group and an alkylene cycloalkylene alkylene group.

[0031] The cycloalkylenealkylene group is represented by the following formula. R calkylene -R alkylene - (Where R calkylene R represents a cycloalkylene group. alkylene represents an alkylene group. )

[0032] The alkylenecycloalkylenealkylene group is represented by the following formula. -R alkylene -R calkylene -R alkylene - (Where R calkylene R represents a cycloalkylene group. alkylene represents an alkylene group. )

[0033] The aromatic group (aryl group, arylene group) may be substituted or unsubstituted. Examples of the substituent of the aromatic group include an alkyl group, a thioalkyl group, a thioaryl group, and a carbonylaryl group.

[0034] Examples of the aryl group include a monocyclic aryl group and a condensed ring aryl group.

[0035] Examples of the monocyclic aryl group include phenyl, tolyl, and mesityl.

[0036] Examples of the fused ring aryl group include naphthyl and the like.

[0037] Examples of the arylene group include a monocyclic arylene group and a condensed ring arylene group.

[0038] Examples of the monocyclic arylene group include a phenylene group and a tolylene group.

[0039] Examples of the fused ring arylene group include naphthylene and the like.

[0040] [Active energy ray-curable composition: composition] The present disclosure relates to an active energy ray-curable composition. The active energy ray-curable composition comprises: a compound A and a compound B, The double bond equivalent of the compound A is greater than 200 g / eq, The double bond equivalent of the compound B is greater than 28 g / eq and less than 200 g / eq, The double bond equivalent of the active energy ray-curable composition as a whole is less than 365 g / eq, The amount of dissolved oxygen relative to 100% by volume of the dissolved gas is greater than 10% by volume. With respect to the entire active energy ray-curable composition, The iron atom content is 400 ppb or less, and the copper atom content is 300 ppb or less.

[0041] <Compound A: Double bond equivalent = 200 g / eq or more> The double bond equivalent of compound A is 200 g / eq or more. Compound A may be used alone or in combination of two or more.

[0042] The "double bond equivalent" refers to a calculated value (g / eq) of the mass per 1 mol of polymerizable double bonds.

[0043] When the monomer composition is known, the double bond equivalent (polymer) is calculated by the following formula. Double bond equivalent = mass of all monomers / amount of polymerizable double bonds contained in the polymer

[0044] Even when the monomer composition is unknown, the double bond equivalent (polymer) can be determined by infrared spectroscopy or Raman spectroscopy by comparison with a calibration curve of a substance with a known double bond equivalent.

[0045] Double bond equivalent (compound A) includes, for example, 1200 g / eq, 1100 g / eq, 1033 g / eq, 1000 g / eq, 900 g / eq, 860 g / eq, 800 g / eq, 700 g / eq, 600 g / eq, 582 g / eq, 550 g / eq, 500 g / eq, 497 g / eq, 450 g / eq, 400 g / eq, 360 g / eq, 300 g / eq, 280 g / eq, 216 g / eq, 200 g / eq, etc. In one embodiment, the double bond equivalent is preferably 200 g / eq or more, more preferably 200 g / eq to 1200 g / eq, and further preferably 450 g / eq to 900 g / eq.

[0046] Examples of the compound A include polymer poly(meth)acrylate and double bond-containing silicone.

[0047] (Polymer poly(meth)acrylate) The "polymer multi-(meth)acrylate" refers to a polymer having two or more (meth)acryloyl groups.

[0048] <Part containing double bonds> Examples of the mole % content (double bond-containing portion / polymer multi-(meth)acrylate) include 50 mol %, 45 mol %, 40 mol %, 35 mol %, 30 mol %, 25 mol %, 20 mol %, 15 mol %, 10 mol %, 5 mol %, etc. In one embodiment, the content is preferably 5 mol % to 50 mol %.

[0049] Examples of the mass % content (double bond-containing portion / polymer multi-(meth)acrylate) include 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 to 50 mass %.

[0050] <Alkyl (meth)acrylate unit> In one embodiment, the polymer multi-(meth)acrylate may include an alkyl (meth)acrylate unit. The alkyl (meth)acrylate unit may be included alone or in combination of two or more.

[0051] Examples of the alkyl (meth)acrylate include linear alkyl (meth)acrylate, branched alkyl (meth)acrylate, and cycloalkyl (meth)acrylate.

[0052] Examples of the linear alkyl (meth)acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, n-hexyl (meth)acrylate, n-heptyl (meth)acrylate, n-octyl (meth)acrylate, n-hexadecyl (meth)acrylate, n-dodecyl (meth)acrylate, n-octadecyl (meth)acrylate, n-eicosyl (meth)acrylate, and n-docosyl (meth)acrylate.

[0053] Examples of the branched alkyl (meth)acrylate include isopropyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate.

[0054] Examples of the cycloalkyl (meth)acrylate include cyclopentyl (meth)acrylate (Siclopentyl (meth)acrylate), cyclohexyl (meth)acrylate, cyclopentyl (meth)acrylate (Siclopentanil (meth)acrylate), and isobornyl (meth)acrylate.

[0055] The mole % content (alkyl (meth)acrylate unit / polymer multi-(meth)acrylate) is exemplified by 95 mol%, 90 mol%, 85 mol%, 80 mol%, 75 mol%, 70 mol%, 65 mol%, 60 mol%, 55 mol%, 50 mol%, 45 mol%, 40 mol%, 35 mol%, 30 mol%, 25 mol%, 20 mol%, 15 mol%, 10 mol%, 5 mol%, 0 mol%, etc. In one embodiment, the content is preferably 0 mol% to 95 mol%.

[0056] The mass % content (alkyl (meth)acrylate unit / polymer multi-(meth)acrylate) is exemplified by 95 mass %, 90 mass %, 85 mass %, 80 mass %, 75 mass %, 70 mass %, 65 mass %, 60 mass %, 55 mass %, 50 mass %, 45 mass %, 40 mass %, 38 mass %, 35 mass %, 30 mass %, 25 mass %, 20 mass %, 15 mass %, 10 mass %, 5 mass %, 0 mass %, etc. In one embodiment, the content is preferably 0 mass % to 95 mass %.

[0057] <Silicone (meth)acrylate unit> In one embodiment, the polymer multi-(meth)acrylate may include silicone (meth)acrylate units. The silicone (meth)acrylate units may be included alone or in combination of two or more.

[0058] In one embodiment, silicone (meth)acrylate is represented by the following formula.

AS1

[0059] Examples of commercially available products ((meth)acrylate silicone esters) include X-22-2426 (manufactured by Shin-Etsu Silicone Co., Ltd.), X-22-174D (manufactured by Shin-Etsu Chemical Co., Ltd.), and Silicone FM-071 1. FM-0721, FM-0725 (manufactured by JNC Corporation), etc.

[0060] The mole % content ((meth)acrylate silicone unit / polymer multi-(meth)acrylate) is exemplified by 50 mol%, 45 mol%, 40 mol%, 35 mol%, 30 mol%, 25 mol%, 20 mol%, 15 mol%, 10 mol%, 5 mol%, 0 mol%, etc. In one embodiment, the content is preferably 0 mol% to 50 mol%.

[0061] The mass % content ((meth)acrylate silicone unit / polymer multi-(meth)acrylate) is exemplified by 50 mass %, 45 mass %, 40 mass %, 35 mass %, 30 mass %, 25 mass %, 20 mass %, 15 mass %, 10 mass %, 5 mass %, 0 mass %, etc. In one embodiment, the content is preferably 0 mass % to 50 mass %.

[0062] <Production Method (Polymer Poly(Meth)acrylate)> Examples of the production method (polymer poly(meth)acrylate) include a method of reacting an α-functional group-containing polymer with a β-functional group-containing polymerizable unsaturated compound.

[0063] Examples of the combination (α-functional group and β-functional group) include the following.

Table A

[0064] Examples of the carboxyl group-containing polymerizable unsaturated compound include (meth)acrylic acid and crotonic acid.

[0065] Examples of the epoxy group-containing polymerizable unsaturated compound include glycidyl (meth)acrylate and β-methylglycidyl (meth)acrylate.

[0066] Examples of the hydroxyl group-containing polymerizable unsaturated compound include 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate.

[0067] Examples of the isocyanate group-containing polymerizable unsaturated compound include 2-isocyanateethyl (meth)acrylate and the like.

[0068] In one embodiment, the production temperature (α-functional group-containing polymer) is preferably 80°C to 140°C.

[0069] Examples of the polymerization solvent (α-functional group-containing polymer) include toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, cyclohexanone, ethylene dichloride, and carbon tetrachloride.

[0070] In one embodiment, the production temperature (polymer poly(meth)acrylate) is preferably 80°C to 120°C.

[0071] Examples of the reaction solvent (polymer poly(meth)acrylate) include methyl isobutyl ketone and butyl acetate.

[0072] (Silicone containing double bonds) The double bond-containing silicones may be used alone or in combination of two or more.

[0073] In one embodiment, the double bond-containing silicone is represented by the following formula.

Chemistry S1

[0074] In one embodiment, the double bond-containing silicone is represented by the following formula.

Chemical S2

[0075] Examples of the group containing a polymerizable double bond include a vinyl group-containing group and a (meth)acryloyl group-containing group. Examples of the group containing a polymerizable double bond include a group in which the following substituents are combined with a vinyl group or a (meth)acryloyl group.

[0076] Examples of the substituent include an alkyl group, an alkylene group, an aryl group, an arylene group, an ether group, an ester group, a hydroxyl group, a keto group, and a group formed by combining these groups.

[0077] In one embodiment, S1 is preferably an integer of 0 or more, more preferably an integer of 0-10.

[0078] In one embodiment, S2 is preferably an integer of 1 or more, more preferably an integer of 0-270.

[0079] In one embodiment, S3 is preferably an integer of 0 or more, more preferably an integer of 0-5.

[0080] In one embodiment, compound A preferably includes a silicone chain-containing compound, more preferably includes a polymer multi(meth)acrylate containing a (meth)silicone acrylate unit, and a silicone containing a double bond, and further preferably includes a polymer multi(meth)acrylate containing a (meth)dimethylpolysiloxane (meth)acrylate unit, and a dimethylpolysiloxane containing a double bond.

[0081] The mass % content (compound A / active energy ray-curable composition non-volatile component) 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 %, 4 mass %, 2 mass %, 1 mass %, 0.75 mass %, 0.5 mass %, 0.1 mass %, 0.05 mass %, etc. In one embodiment, the content is preferably 0.05 mass % to 99 mass %, more preferably 0.1 mass % to 2 mass %.

[0082] The mass % content (compound A / active energy ray curable compound) 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 %, 4 mass %, 2 mass %, 1 mass %, 0.75 mass %, 0.5 mass %, 0.1 mass %, 0.05 mass %, etc. In one embodiment, the content is preferably 0.05 mass % to 99 mass %, more preferably 0.1 mass % to 2 mass %.

[0083] <Compound B: Double bond equivalent = 28 g / eq or more and less than 200 g / eq> The double bond equivalent of compound B is 28 g / eq or more and less than 200 g / eq. Compound B may be used alone or in combination of two or more.

[0084] Examples of the compound B include (poly)(meth)acrylates not containing a urethane bond and urethane (poly)(meth)acrylates.

[0085] Examples of the number of polymerizable double bonds (compound B) include 20, 19, 18, 17, 16, 15, 14, 13, 12, 11, 10, 9, 8, 7, 6, 5, 4, 3, 2, and 1. In one embodiment, the number is preferably 1 to 20.

[0086] <(Poly)(meth)acrylate not containing urethane bond> The (poly)(meth)acrylate not containing a urethane bond may be used alone or in combination of two or more.

[0087] Examples of the (poly)(meth)acrylates not containing a urethane bond include (poly)pentaerythritol (poly)(alkylene oxide-modified or epoxy-modified) (meth)acrylate, (poly)trimethylolpropane (poly)(alkylene oxide-modified or epoxy-modified) (meth)acrylate, (poly)glycerol (poly)(alkylene oxide-modified or epoxy-modified) (meth)acrylate, isocyanurate structure-containing (poly)(alkylene oxide-modified or epoxy-modified) (meth)acrylate, (poly)alkylene (poly)(alkylene oxide-modified or epoxy-modified) (meth)acrylate, and bisphenol A (poly)(alkylene oxide-modified or epoxy-modified) (meth)acrylate.

[0088] “(Alkylene oxide-modified or epoxy-modified) (meth)acrylate” means “alkylene oxide-modified (meth)acrylate and / or epoxy-modified (meth)acrylate”.

[0089] <(Poly)pentaerythritol (poly)(alkylene oxide-modified or epoxy-modified)(meth)acrylate> (Poly)pentaerythritol (poly)(alkylene oxide-modified or epoxy-modified) (meth)acrylate is a compound represented by formula (A′) or the like.

Chemical A1

Chemical A2

Chemical A3

[0090] In addition, "the groups may be different for each structural unit" means that in formula (A'), for example, when n is 2, [Chem. A4] R b4A With R b4B Can be different groups, R b5A With R b5B Can be different groups.

[0091] Examples of pentaerythritol poly(meth)acrylates include pentaerythritol (meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, and pentaerythritol tetra(meth)acrylate.

[0092] Examples of the pentaerythritol (poly)alkylene oxide-modified (meth)acrylate include pentaerythritol ethylene oxide-modified (meth)acrylate, pentaerythritol di(ethylene oxide-modified (meth)acrylate), pentaerythritol tri(ethylene oxide-modified (meth)acrylate), pentaerythritol tetra(ethylene oxide-modified (meth)acrylate), pentaerythritol di(propylene oxide-modified (meth)acrylate), pentaerythritol tri(propylene oxide-modified (meth)acrylate), and pentaerythritol tetra(propylene oxide-modified (meth)acrylate).

[0093] Examples of the pentaerythritol (poly)epoxy-modified (meth)acrylate include pentaerythritol epoxy (meth)acrylate, pentaerythritol diepoxy (meth)acrylate, pentaerythritol triepoxy (meth)acrylate, and pentaerythritol tetraepoxy (meth)acrylate.

[0094] Examples of the polypentaerythritol (poly)(meth)acrylate include dipentaerythritol (meth)acrylate, dipentaerythritol di(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol (meth)acrylate, tripentaerythritol di(meth)acrylate, tripentaerythritol tri(meth)acrylate, tripentaerythritol tetra(meth)acrylate, tripentaerythritol penta(meth)acrylate, tripentaerythritol hexa(meth)acrylate, tripentaerythritol hepta(meth)acrylate, and tripentaerythritol octa(meth)acrylate.

[0095] Examples of the polypentaerythritol (poly) alkylene oxide-modified (meth)acrylate include dipentaerythritol (ethylene oxide-modified (meth)acrylate), 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), and dipentaerythritol octa(ethylene oxide-modified (meth)acrylate). ) 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 ethylene 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 heptath(ethylene oxide modified (meth)acrylate), tripentaerythritol octa(ethylene oxide modified (meth)acrylate), tripentaerythritol di( propylene oxide modified (meth) acrylate), tripentaerythritol tri(propylene oxide modified (meth) acrylate), tripentaerythritol tetra(propylene oxide modified (meth) acrylate), tripentaerythritol penta(propylene oxide modified (meth) acrylate), tripentaerythritol hexa(propylene oxide modified (meth) acrylate), tripentaerythritol heptath(propylene oxide modified (meth) acrylate), tripentaerythritol octa(propylene oxide modified (meth) acrylate), etc.

[0096] Examples of the polypentaerythritol (poly)epoxy-modified (meth)acrylate include dipentaerythritol epoxy (meth)acrylate, dipentaerythritol diepoxy (meth)acrylate, dipentaerythritol triepoxy (meth)acrylate, dipentaerythritol tetraepoxy (meth)acrylate, dipentaerythritol pentaepoxy (meth)acrylate, dipentaerythritol hexaepoxy (meth)acrylate, tripentaerythritol epoxy (meth)acrylate, tripentaerythritol diepoxy (meth)acrylate, tripentaerythritol triepoxy (meth)acrylate, tripentaerythritol tetraepoxy (meth)acrylate, tripentaerythritol pentaepoxy (meth)acrylate, tripentaerythritol hexaepoxy (meth)acrylate, tripentaerythritol heptaepoxy (meth)acrylate, and tripentaerythritol octaepoxy (meth)acrylate.

[0097] <(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 B1

Chemical B2

Chemical B3

[0098] Examples of the trimethylolpropane (poly) (meth)acrylate include trimethylolpropane (meth)acrylate, trimethylolpropane di(meth)acrylate, and trimethylolpropane tri(meth)acrylate.

[0099] Examples of trimethylolpropane (poly)alkylene oxide-modified (meth)acrylates include trimethylolpropane ethylene oxide-modified (Meth)acrylate, trimethylolpropane di(ethylene oxide-modified (meth)acrylate), trimethylolpropane tri(ethylene oxide-modified (meth)acrylate), trimethylolpropane propylene oxide-modified (meth)acrylate, trimethylolpropane di(propylene oxide-modified (meth)acrylate), trimethylolpropane tri(propylene oxide-modified (meth)acrylate), and the like.

[0100] Examples of the trimethylolpropane (poly)epoxy-modified (meth)acrylate include trimethylolpropane epoxy (meth)acrylate, trimethylolpropane diepoxy (meth)acrylate, and trimethylolpropane triepoxy (meth)acrylate.

[0101] Examples of the polytrimethylolpropane (poly) (meth)acrylate include di-trimethylolpropane (meth)acrylate, di-trimethylolpropane di(meth)acrylate, di-trimethylolpropane tri(meth)acrylate, and di-trimethylolpropane tetra(meth)acrylate.

[0102] Examples of the polytrimethylolpropane (poly)alkylene oxide-modified (meth)acrylate include di-trimethylolpropane ethylene oxide-modified (meth)acrylate, di-trimethylolpropane di(ethylene oxide-modified (meth)acrylate), di-trimethylolpropane tri(ethylene oxide-modified (meth)acrylate), di-trimethylolpropane tetra(ethylene oxide-modified (meth)acrylate), di-trimethylolpropane propylene oxide-modified (meth)acrylate, di-trimethylolpropane di(propylene oxide-modified (meth)acrylate), di-trimethylolpropane tri(propylene oxide-modified (meth)acrylate), and di-trimethylolpropane tetra(propylene oxide-modified (meth)acrylate).

[0103] Examples of the polytrimethylolpropane (poly)epoxy-modified (meth)acrylate include di-trimethylolpropane epoxy (meth)acrylate, di-trimethylolpropane diepoxy (meth)acrylate, di-trimethylolpropane triepoxy (meth)acrylate, and di-trimethylolpropane tetraepoxy (meth)acrylate.

[0104] <(Poly)glycerol (poly)(alkylene oxide-modified or epoxy-modified)(meth)acrylate> (Poly)glycerol (poly)(alkylene oxide-modified or epoxy-modified) (meth)acrylate is a compound represented by formula (C′) or the like.

Chemical C1

Chemical C2

Chemical C3

[0105] Examples of glycerol (poly) (meth)acrylate include glycerol (meth)acrylate, glycerol di(meth)acrylate, and glycerol tri(meth)acrylate.

[0106] Examples of the glycerol (poly)alkylene oxide-modified (meth)acrylate include glycerol ethylene oxide-modified (meth)acrylate, glycerol di(ethylene oxide-modified (meth)acrylate), glycerol tri(ethylene oxide-modified (meth)acrylate), glycerol di(propylene oxide-modified (meth)acrylate), and glycerol tri(propylene oxide-modified (meth)acrylate).

[0107] Examples of the glycerin (poly)epoxy-modified (meth)acrylate include glycerin epoxy (meth)acrylate, glycerin diepoxy (meth)acrylate, and glycerin triepoxy (meth)acrylate.

[0108] Examples of the polyglycerol (poly) (meth)acrylate include diglycerol (meth)acrylate, diglycerol di(meth)acrylate, diglycerol tri(meth)acrylate, diglycerol tetra(meth)acrylate, triglycerol (meth)acrylate, triglycerol di(meth)acrylate, triglycerol tri(meth)acrylate, triglycerol tetra(meth)acrylate, and triglycerol penta(meth)acrylate.

[0109] Examples of polyglycerol (poly) alkylene oxide-modified (meth)acrylates include diglycerol ethylene oxide-modified (meth)acrylate, diglycerol di(ethylene oxide-modified (meth)acrylate), diglycerol tri(ethylene oxide-modified (meth)acrylate), diglycerol tetra(ethylene oxide-modified (meth)acrylate), triglycerol 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), and polyglycerol (poly)alkylene oxide-modified (meth)acrylate. (meth)acrylate), diglycerol propylene 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 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.

[0110] Examples of the polyglycerol (poly)epoxy-modified (meth)acrylate include diglycerol epoxy (meth)acrylate, diglycerol diepoxy (meth)acrylate, diglycerol triepoxy (meth)acrylate, diglycerol tetraepoxy (meth)acrylate, triglycerol epoxy (meth)acrylate, triglycerol diepoxy (meth)acrylate, triglycerol triepoxy (meth)acrylate, triglycerol tetraepoxy (meth)acrylate, and triglycerol pentaepoxy (meth)acrylate.

[0111] <(Poly)(alkylene oxide-modified or epoxy-modified)(meth)acrylate containing isocyanurate structure> The (poly)(alkylene oxide-modified or epoxy-modified) (meth)acrylate containing an isocyanurate structure is a compound represented by the formula (D′) or the like.

Chemical D1

Chemical D2

Chemical D3

[0112] Examples of the (poly) (meth) acrylate containing an isocyanurate structure include isocyanuric acid (meth) acrylate, isocyanuric acid di(meth) acrylate, and isocyanuric acid tri(meth) acrylate.

[0113] Examples of the (poly)alkylene oxide-modified (meth)acrylate containing an isocyanurate structure include isocyanuric acid ethylene oxide-modified (meth)acrylate, isocyanuric acid di(ethylene oxide-modified (meth)acrylate), and isocyanuric acid tri(ethylene oxide-modified (meth)acrylate).

[0114] Examples of the (poly)epoxy-modified (meth)acrylate containing an isocyanurate structure include isocyanuric acid epoxy-modified (meth)acrylate, isocyanuric acid diepoxy-modified (meth)acrylate, and isocyanuric acid triepoxy-modified (meth)acrylate.

[0115] <(Poly)alkylene (poly) (alkylene oxide-modified or epoxy-modified) (meth)acrylate> <(Poly)alkylene (poly)(alkylene oxide-modified or epoxy-modified) (meth)acrylate> is a compound represented by the formula (E') or the like.

Chemical E1

Chemical E2

Chemistry E3

[0116] Examples of the (poly)alkylene (poly) (alkylene oxide-modified or epoxy-modified) (meth)acrylate include alkylene di(meth)acrylates, alkylene diepoxy-modified (meth)acrylates, alkylene diepoxy-modified (meth)acrylates, polyalkylene glycol di(meth)acrylates, polyalkylene glycol diepoxy-modified (meth)acrylates, polyalkylene glycol diepoxy-modified (meth)acrylates, and the like.

[0117] Examples of the alkylene di(meth)acrylate include 1,2-ethylene glycol di(meth)acrylate, 1,3-propylene glycol di(meth)acrylate, 1,4-butylene glycol di(meth)acrylate, 1,5-pentanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,7-heptanediol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, and neopentyl glycol di(meth)acrylate.

[0118] Examples of the alkylene dialkylene oxide-modified (meth)acrylate include 1,2-ethylene glycol di(ethylene oxide-modified (meth)acrylate), 1,3-propylene glycol di(ethylene oxide-modified (meth)acrylate), 1,4-butylene glycol di(ethylene oxide-modified (meth)acrylate), 1,5-pentanediol di(ethylene oxide-modified (meth)acrylate), 1,6-hexanediol di(ethylene oxide-modified (meth)acrylate), 1,7-heptanediol di(ethylene oxide-modified (meth)acrylate), 1,8-octanediol di(ethylene oxide-modified (meth)acrylate), 1,9-nonanediol di(ethylene oxide-modified (meth)acrylate), 1,10-decanediol di(ethylene oxide-modified (meth)acrylate), neopentyl glycol di(ethylene oxide-modified (meth)acrylate), and 1,6-hexanediol di(ethylene oxide-modified (meth)acrylate). (meth)acrylate), 1,2-ethylene glycol di(propylene oxide modified (meth)acrylate), 1,3-propylene glycol di(propylene oxide modified (meth)acrylate), 1,4-butylene glycol di(propylene oxide modified (meth)acrylate), 1,5-pentanediol di(propylene oxide modified (meth)acrylate), 1,6-hexanediol di(propylene oxide modified (meth)acrylate), 1,7-heptanediol di(propylene oxide modified (meth)acrylate), 1,8-octanediol di(propylene oxide modified (meth)acrylate), 1,9-nonanediol di(propylene oxide modified (meth)acrylate), 1,10-decanediol di(propylene oxide modified (meth)acrylate), neopentyl glycol di(propylene oxide modified (meth)acrylate), etc.

[0119] Examples of the alkylene diepoxy-modified (meth)acrylate include 1,2-ethylene glycol diepoxy (meth)acrylate, 1,3-propylene glycol diepoxy (meth)acrylate, 1,4-butylene glycol diepoxy (meth)acrylate, 1,5-pentanediol diepoxy (meth)acrylate, 1,6-hexanediol diepoxy (meth)acrylate, 1,7-heptanediol diepoxy (meth)acrylate, 1,8-octanediol diepoxy (meth)acrylate, 1,9-nonanediol diepoxy (meth)acrylate, 1,10-decanediol diepoxy (meth)acrylate, and neopentyl glycol diepoxy (meth)acrylate.

[0120] Examples of the polyalkylene glycol di(meth)acrylate include diethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, and tripropylene glycol di(meth)acrylate.

[0121] Examples of the polyalkylene glycol dialkylene oxide-modified (meth)acrylate include diethylene glycol di(ethylene oxide-modified (meth)acrylate), dipropylene glycol di(ethylene oxide-modified (meth)acrylate), triethylene glycol di(ethylene oxide-modified (meth)acrylate), and tripropylene glycol di(ethylene oxide-modified (meth)acrylate).

[0122] Examples of the polyalkylene glycol diepoxy-modified (meth)acrylate include diethylene glycol diepoxy (meth)acrylate, dipropylene glycol diepoxy (meth)acrylate, triethylene glycol diepoxy (meth)acrylate, and tripropylene glycol diepoxy (meth)acrylate.

[0123] <Bisphenol A (poly)(alkylene oxide-modified or epoxy-modified)(meth)acrylate> Bisphenol A (poly)(alkylene oxide-modified or epoxy-modified) (meth)acrylate is a compound represented by formula (F′) or the like.

Chemistry F1

Chemistry F2

Chemistry F3

[0124] Examples of the bisphenol A (poly) (meth) acrylate include bisphenol A (meth) acrylate and bisphenol A di (meth) acrylate.

[0125] Examples of the bisphenol A (poly)alkylene oxide-modified (meth)acrylate include bisphenol A ethylene oxide-modified (meth)acrylate, bisphenol A di(ethylene oxide-modified (meth)acrylate), bisphenol A propylene oxide-modified (meth)acrylate, and bisphenol A di(propylene oxide-modified (meth)acrylate).

[0126] Examples of the bisphenol A (poly)epoxy-modified (meth)acrylate include bisphenol A epoxy-modified (meth)acrylate and bisphenol A diepoxy-modified (meth)acrylate.

[0127] <Urethane (poly) (meth)acrylate> The urethane (poly) (meth)acrylates may be used alone or in combination of two or more.

[0128] Examples of the urethane (poly) (meth) acrylate include a reaction product of a compound group consisting of a hydroxyl group-containing (poly) (meth) acrylate and a polyisocyanate.

[0129] <Hydryl-containing (poly)(meth)acrylate> Examples of the hydroxyl-containing (poly)(meth)acrylate include hydroxyl-containing (poly)pentaerythritol (poly)(meth)acrylate, hydroxyl-containing (poly)trimethylolpropane (poly)(meth)acrylate, and hydroxyl-containing (poly)glycerol (poly)(meth)acrylate.

[0130] <Polyisocyanate> The polyisocyanate may be used alone or in combination of two or more.

[0131] “Polyisocyanate” refers to a compound having two or more isocyanate groups (—N═C═O).

[0132] Examples of the polyisocyanate include linear aliphatic polyisocyanate, branched aliphatic polyisocyanate, alicyclic polyisocyanate, aromatic polyisocyanate, and biuret forms, isocyanurate forms, allophanate forms, and adduct forms thereof.

[0133] Examples of the linear aliphatic polyisocyanate include methylene diisocyanate, dimethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, octamethylene diisocyanate, nonamethylene diisocyanate and decamethylene diisocyanate.

[0134] Examples of the branched aliphatic polyisocyanate include diethylpentylene diisocyanate, trimethylbutylene diisocyanate, trimethylpentylene diisocyanate, and trimethylhexamethylene diisocyanate.

[0135] Examples of the alicyclic polyisocyanate include monocyclic alicyclic polyisocyanate, bridged alicyclic polyisocyanate, and condensed alicyclic polyisocyanate.

[0136] Examples of the monocyclic alicyclic polyisocyanate include hydrogenated xylene diisocyanate, isophorone diisocyanate, cyclopentylene diisocyanate, cyclohexylene diisocyanate, cycloheptylene diisocyanate, cyclodecylene diisocyanate, 3,5,5-trimethylcyclohexylene diisocyanate, and dicyclohexylmethane diisocyanate.

[0137] Examples of the bridged alicyclic polyisocyanate include tricyclodecylene diisocyanate, adamantane diisocyanate, and norbornene diisocyanate.

[0138] Examples of the condensed-ring alicyclic polyisocyanate include bicyclodecylene diisocyanate and the like.

[0139] Examples of the aromatic polyisocyanate include monocyclic aromatic polyisocyanate and condensed-ring aromatic polyisocyanate.

[0140] Examples of the monocyclic aromatic polyisocyanate include 4,4′-diphenyldimethylmethane diisocyanate, 4,4′-diphenyltetramethylmethane diisocyanate, 4,4′-diphenylmethane diisocyanate, 4,4′-diphenylmethane diisocyanate, 4,4′-dibenzyl diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, toluene diisocyanate, xylylene diisocyanate, and tetramethyl-meta-xylylene diisocyanate.

[0141] Examples of the condensed ring aromatic polyisocyanate include 1,5-naphthalene diisocyanate and the like.

[0142] In one embodiment, the compound B is preferably (poly)pentaerythritol (poly)(alkylene oxide-modified or epoxy-modified) (meth)acrylate, more preferably polypentaerythritol poly(meth)acrylate, and further preferably dipentaerythritol poly(meth)acrylate.

[0143] The mass % content (compound B / active energy ray-curable composition non-volatile component) includes, for example, 90 mass %, 85 mass %, 81 mass %, 80 mass %, 78 mass %, 75 mass %, 70 mass %, 69 mass %, 68 mass %, 65 mass %, 60 mass %, 55 mass %, 50 mass %, 45 mass %, 40 mass %, 35 mass %, 30 mass %, 25 mass %, 20 mass %, 15 mass %, 10 mass %, 5 mass %, 0 mass %, etc. In one embodiment, the content is preferably 0 mass % to 90 mass %.

[0144] The mass % content (compound B / active energy ray-curable compound) 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 0 mass % to 90 mass %.

[0145] <Double bond equivalent (active energy ray-curable composition as a whole)> The double bond equivalent (as a whole active energy ray-curable composition) is, for example, less than 365 g / eq, 364 g / eq, 360 g / eq, 350 g / eq, 300 g / eq, 275 g / eq, 250 g / eq, 225 g / eq, 216 g / eq, 202 g / eq, 200 g / eq, 186 g / eq, 175 g / eq, 150 g / eq, 125 g / eq, 116 g / eq, 112 g / eq, 105 g / eq, 104 g / eq, 101 g / eq, 100 g / eq, 98 g / eq, 97 g / eq, 90 g / eq, 86 g / eq, 85 g / eq, 75 g / eq, 50 g / eq, 28 g / eq, etc. In one embodiment, the double bond equivalent is preferably less than 365 g / eq, more preferably 28 g / eq or more and less than 365 g / eq, further preferably 85 g / eq to 360 g / eq, and particularly preferably 90 g / eq to 125 g / eq.

[0146] The double bond equivalent (the entire active energy ray-curable composition) is a weighted average value. Specifically, when the active energy ray-curable composition has the following composition, the double bond equivalent (the entire active energy ray-curable composition) is calculated by the following formula. Compound α (double bond equivalent Ag / eq): α mass % Compound β (double bond equivalent Bg / eq): β mass % Weighted average = A×(α / 100)+B×(β / 100)

[0147] <Dissolved oxygen amount relative to 100% by volume of dissolved gas: dissolved oxygen amount> The amount of dissolved oxygen relative to 100% by volume of the dissolved gas in the active energy ray-curable composition is, for example, less than 20% by volume, 19.9% ​​by volume, 19% by volume, 18% by volume, 17% by volume, 16% by volume, 15% by volume, 14% by volume, 13% by volume, 12% by volume, 11% by volume, 10.1% by volume, or greater than 10% by volume. In one embodiment, the amount of dissolved oxygen is preferably greater than 10% by volume, more preferably greater than 10% by volume and less than 20% by volume, and even more preferably 13% to 19% by volume.

[0148] The amount of dissolved oxygen can be measured under the following conditions. Oxygen concentration meter: O2 sensor InPro6800 / 12 / 320 (manufactured by Metler Toledo Co., Ltd.) Converter: M400 (manufactured by Tororo Co., Ltd.) Measuring temperature: room temperature (20℃~25℃)

[0149] The amount of dissolved oxygen can be adjusted by, for example, bubbling air into the composition.

[0150] <Iron Atom> Examples of the iron atom content relative to the active energy ray-curable composition include 400 ppb, 399 ppb, 375 ppb, 350 ppb, 325 ppb, 300 ppb, 275 ppb, 250 ppb, 225 ppb, 200 ppb, 175 ppb, 150 ppb, 140 ppb, 130 ppb, 125 ppb, 120 ppb, 115 ppb, 110 ppb, 105 ppb, 100 ppb, 95 ppb, 90 ppb, 85 ppb, 80 ppb, 75 ppb, 70 ppb, 65 ppb, 60 ppb, 55 ppb, 50 ppb, 45 ppb, 40 ppb, 35 ppb, 30 ppb, 25 ppb, 20 ppb, 15 ppb, 10 ppb, 5 ppb, and 0 ppb. In one embodiment, the content is preferably 400 ppb or less, and more preferably 150 ppb or less.

[0151] <Copper Atom> The copper atom content relative to the active energy ray-curable composition is, for example, 300 ppb, 275 ppb, 250 ppb, 225 ppb, 200 ppb, 175 ppb, 150 ppb, 140 ppb, 130 ppb, 125 ppb, 120 ppb, 115 ppb, 110 ppb, 105 ppb, 100 ppb, 95 ppb, 90 ppb, 85 ppb, 80 ppb, 75 ppb, 70 ppb, 65 ppb, 60 ppb, 55 ppb, 50 ppb, 45 ppb, 40 ppb, 35 ppb, 30 ppb, 25 ppb, 20 ppb, 15 ppb, 10 ppb, 5 ppb, 0 ppb, etc. In one embodiment, the content is preferably 300 ppb or less, and more preferably 125 ppb or less.

[0152] The iron atoms and copper atoms may be present in the active energy ray-curable composition in various forms such as zero-valent metals and ions.

[0153] The amounts of iron atoms and copper atoms can be adjusted by refining.

[0154] Examples of purification include distillation, washing, and filtration using a metal removal filter.

[0155] The iron atom content and the copper atom content can be measured by the following method. Analysis type: ICP-MS Device Manufacturer: PerkinElmer Device Name: ELAN DRCII Pre-treatment: dilute with 1% nitric acid NMP (N-methyl-2-pyrrolidone) Quantitative method: Absolute quantification by calibration curve method using standard samples Standard sample concentrations for calibration curve: 0ppb, 1ppb, 2ppb, 5ppb, 20ppb, 50ppb Sample concentration: 0.5% (diluted 200 times)

[0156] <Photopolymerization initiator> In one embodiment, the active energy ray-curable composition may optionally include a photopolymerization initiator. The photopolymerization initiator may be used alone or in combination of two or more.

[0157] Examples of the photopolymerization initiator include an α-hydroxydimethylacetophenone group-containing photopolymerization initiator, α-hydroxyphenylcycloalkyl ketone, α-aminophenylalkyl ketone, benzyl dimethyl ketal, unsubstituted or substituted phenylalkyl ketone, unsubstituted or substituted benzil, unsubstituted or substituted benzophenone, acylphosphine oxide, substituted thioxanthone, and oxime ester.

[0158] Examples of the photopolymerization initiator containing an α-hydroxydimethylacetophenone group include 2-hydroxy-2-methyl-1-propiophenone, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-methylpropiophenone, and 2-hydroxy-1-(4-(4-(2-hydroxy-2-methylpropionyl)benzyl)phenyl)-2-methylpropan-1-one.

[0159] Examples of the α-hydroxyphenylcycloalkyl ketone include 1-hydroxycyclohexyl phenyl ketone and the like.

[0160] Examples of α-aminoalkylphenone include 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropane-1-one and the like.

[0161] Examples of benzyl dimethyl ketal include 2,2-dimethoxy-1,2-diphenylethane-1-one.

[0162] Examples of the unsubstituted or substituted alkyl phenone include benzoin methyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin ethyl ether, acetophenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2-phenyl-2-(p-toluenesulfonyloxy)acetophenone, benzoin, 2-benzyl-2-(dimethylamino)-4′-morpholinobutylphenone, 2-methyl-4′-(methylthio)-2-morpholinopropiophenone, 2-isonitrosopropiophenone, and 2,2-dimethoxy-1,2-diphenylethane-1-one.

[0163] Examples of the unsubstituted or substituted benzil include benzil and anisil (p-anisil).

[0164] Examples of the unsubstituted or substituted benzophenone include benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-dichlorobenzophenone, 1,4-dibenzoylbenzene, 2-benzoylbenzoic acid, 4-benzoylbenzoic acid, and methyl 2-benzoylbenzoate.

[0165] Examples of the acylphosphine oxide include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide.

[0166] Examples of the substituted thioxanthone include 2-chlorothioxanthone, 2-isopropylthioxanthone, and 2,4-diethylthioxanthone.

[0167] Examples of oxime esters include 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-carbazole-3-yl]-, 1-(o-acetyl oxime) (i.e., 1-(((1-(9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl)ethylidene)amino)oxy)ethane-1-one, etc.

[0168] When electron beam curing is performed, no photopolymerization initiator is required.

[0169] In one embodiment, as the photopolymerization initiator, preferably, α-aminophenylalkyl ketone is used, and more preferably, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropane-1-one is used.

[0170] The mass % content (photopolymerization initiator / active energy ray-curable composition non-volatile component) includes, for example, 10 mass %, 9 mass %, 8 mass %, 7 mass %, 6 mass %, 5 mass %, 4 mass %, 3 mass %, 2 mass %, 1 mass %, 0 mass %, etc. In one embodiment, the content is preferably 0 mass % to 10 mass %, more preferably 1 mass % to 6 mass %.

[0171] <Organic solvents> In one embodiment, the active energy ray-curable composition may optionally contain an organic solvent. The organic solvent may be used alone or in combination of two or more.

[0172] Examples of the organic solvent include ketone solvents, aromatic solvents, alcohol solvents, glycol solvents, glycol ether solvents, ester solvents, petroleum solvents, alkyl halide solvents, and amide solvents.

[0173] Examples of the ketone solvent include methyl ethyl ketone, acetylacetone, methyl isobutyl ketone, cyclopentanone, and cyclohexanone.

[0174] Examples of the aromatic solvent include toluene and xylene.

[0175] Examples of the alcohol solvent include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, and tert-butanol.

[0176] Examples of the glycol solvent include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, polyethylene glycol, and polypropylene glycol.

[0177] Examples of the glycol ether solvent include ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol monoisopropyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol monoisobutyl ether, and ethylene glycol mono-tert-butyl ether.

[0178] Examples of the ester solvent include ethyl acetate, butyl acetate, methyl cellosolve acetate, ethyl cellosolve acetate, and propylene glycol monomethyl ether acetate.

[0179] Examples of petroleum-based solvents include Sepulchroic #100 (manufactured by Sequoia Co., Ltd.) and Securon Co., Ltd. #150 (manufactured by Seiko Co., Ltd.).

[0180] Examples of the halogenated alkyl solvent include chloroform and the like.

[0181] Examples of the amide solvent include dimethylformamide.

[0182] In one embodiment, the organic solvent preferably includes an alcohol solvent and a ketone solvent, more preferably includes isopropyl alcohol and methyl ethyl ketone, and further preferably includes a combination of isopropyl alcohol and methyl ethyl ketone.

[0183] The mass % content (organic solvent / active energy ray-curable composition) includes, for example, 99 mass %, 98.5 mass %, 98 mass %, 97 mass %, 95 mass %, 90 mass %, 85 mass %, 80 mass %, 75 mass %, 70 mass %, 65 mass %, 60 mass %, 55 mass %, 50 mass %, 45 mass %, 40 mass %, 35 mass %, 30 mass %, 25 mass %, 20 mass %, 15 mass %, 10 mass %, 5 mass %, 0 mass %, etc. In one embodiment, the content is preferably 0 mass % to 99 mass %.

[0184] <Additives> The active energy ray-curable composition may optionally contain an agent (additive) that does not belong to any of the above.

[0185] Examples of the additives include ultraviolet absorbers, defoamers, surface conditioners, antifouling agents, pigments, and the like.

[0186] In one embodiment, the content (additive / active energy ray-curable composition) is preferably less than 5 parts by mass, less than 1 part by mass, less than 0.1 part by mass, less than 0.01 part by mass, or 0 part by mass.

[0187] In one embodiment, the content by mass (additive / compound A), the content by mass (additive / compound B), the content by mass (additive / photopolymerization initiator), and the content by mass (additive / organic solvent) 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.

[0188] The active energy ray-curable composition can be produced by dispersing and mixing the above-mentioned reagents.

[0189] Examples of the dispersing and mixing means include an emulsifying disperser and an ultrasonic dispersing device.

[0190] Examples of the applications (active energy ray-curable composition) include coating agents, hard coating agents, clear coating agents, clear hard coating agents, antiglare coating agents, antiglare hard coating agents, coating agents for optical films, hard coating agents for optical films, release coating agents, release film coating agents, and primers.

[0191] [cured material] The present disclosure relates to a cured product of the active energy ray-curable composition.

[0192] Examples of curing conditions include the following conditions.

[0193] [Laminate] The present disclosure relates to a laminate comprising the cured product.

[0194] As a production method (laminate), for example, there is mentioned 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 surface of the substrate Active energy ray curing step: a step of forming a cured product layer of the active energy ray curable composition by irradiating the substrate with active energy ray

[0195] Examples of the substrate include polycarbonate films, acrylic films (polymethyl methacrylate films, etc.), polystyrene films, polyester films, polyolefin films, epoxy resin films, melamine resin films, triacetyl cellulose films, ABS films, AS films, norbornene-based resin films, cyclic olefin films, and polyvinyl alcohol films.

[0196] In one embodiment, the thickness (substrate) is preferably 10 μm to 2000 μm.

[0197] In one embodiment, the thickness (cured material layer) is preferably 0.05 μm to 20 μm.

[0198] (Coating process) Examples of the coating method include rod coater coating, wire bar coating, Mayer bar coating, air knife coating, gravure coating, reverse gravure coating, flow coater coating, offset printing, flexographic printing, and screen printing.

[0199] (Active energy ray curing process) Examples of active energy rays include ultraviolet rays and electron beams.

[0200] Examples of the ultraviolet light source include a xenon lamp, a high-pressure mercury lamp, and a metal halide lamp.

[0201] When a high-pressure mercury lamp is used, preferred curing conditions include the following conditions. Lamp output: 25W / cm~160W / cm UV illumination: 10mW / cm 2 ~800mW / cm 2 Accumulated light intensity: 5mJ / cm 2 ~2000mJ / cm 2 Conveying speed: 1m / min~50m / min

[0195] When an electron beam is used, the following conditions are preferably mentioned as curing conditions. Accelerating voltage: 10kV~300kV Conveying speed: 5m / min~50m / min [Example]

[0203] The present invention is specifically described below by examples and comparative examples. However, the above description and the following examples are not recorded for the purpose of limiting the present invention. The present invention is limited only by the scope of the claims. Unless otherwise specified, the numerical values ​​such as parts and % are based on mass.

[0204] Preparation Example 1 Polymer poly(meth)acrylate Into a four-necked flask equipped with a stirrer, a thermometer, a reflux cooler, and a nitrogen inlet, 125 parts of butyl acetate, 100 parts of glycidyl methacrylate (GMA), and 1 part of azobisisobutyronitrile (AIBN) were added, stirred, heated to 100° C. under a nitrogen stream, and reacted for 10 hours. After the reaction was completed, it was cooled to 60° C., 50 parts of acrylic acid (AA), 0.1 parts of triphenylphosphine, and 0.05 parts of p-methoxyphenol were added, the nitrogen inlet was replaced with an air bubbling device, and air was bubbled into the reaction liquid while stirring, and the temperature was raised to 110° C. and kept warm for 9 hours to obtain a polymer multi-(meth)acrylate (non-volatile content 50%).

[0205] Unless otherwise specified, other examples were carried out in the same manner as described above except for changes as shown in the following table.

[0206] [Table 1] FM-0721: Silicone methacrylate, number average molecular weight 5000, manufactured by JNS Co., Ltd.

EX1

[0207] Example 1 Active Energy Ray Curable Composition After mixing the substances described in the following table as non-volatile components, dilute with a mixed solvent of isopropyl alcohol / methyl ethyl ketone = 70% / 30% (non-volatile component 40%). Next, use Zeta Plus activated carbon adsorption depth filter R53S (manufactured by 3M) to filter the obtained active energy line curable composition. The dissolved oxygen content is adjusted by blowing air into the composition. After filtering, the iron atom content and the copper atom content are adjusted by adding iron salts and copper salts as needed.

[0208] Unless otherwise specified, other examples were carried out in the same manner as described above except for changes as shown in the following table.

[0209] [Table 2] [Table 3]

Table 4

Table 5

EX2

[0210] The amount of dissolved oxygen was measured under the following conditions. Oxygen concentration meter: O2 sensor InPro6800 / 12 / 320 (manufactured by Metler Toledo Co., Ltd.) Converter: M400 (manufactured by Tororo Co., Ltd.) Measuring temperature: room temperature (20℃~25℃)

[0211] The iron atom and copper atom contents were measured by the following method. Analysis type: ICP-MS Device Manufacturer: PerkinElmer Device Name: ELAN DRCII Pre-treatment: dilute with 1% nitric acid NMP (N-methyl-2-pyrrolidone) Quantitative method: Absolute quantification by calibration curve method using standard samples Standard sample concentrations for calibration curve: 0ppb, 1ppb, 2ppb, 5ppb, 20ppb, 50ppb Sample concentration: 0.5% (diluted 200 times)

[0212] (stability) The active energy ray-curable composition was stored at 20° C., and the number of days until gelation was measured. A: There is still no gelation after 6 months. B: Gel formation occurred after 5 months and less than 6 months. C: Gel formation after 4 months and less than 5 months. D: Gel formation in less than 4 months.

[0213] Manufacturing (laminate) The active energy ray-curable composition was applied to a polyethylene terephthalate film (thickness: 100 μm) using a bar coater #12 (film thickness: 3 μm after drying), dried at 80°C for 1 minute, and then irradiated with active energy rays (ultraviolet irradiation, illumination: 520 mw / cm 2 , cumulative light intensity: 500mJ / cm 2 ) to obtain a laminate.

[0214] (Curing property) A cotton swab soaked in methyl ethyl ketone was rubbed back and forth on the surface of the cured product, and the cured product was visually observed and evaluated according to the following criteria. A: After 20 reciprocating cycles, no change in the solidified material was observed. B: After 20 reciprocating strokes, whitening of the cured product was observed. C: After 10 reciprocating strokes, whitening of the cured product was observed. D: After 5 reciprocations, whitening of the cured product was observed.

[0215] (Pollution resistance) The surface of the cured product was written with an oil-based marker pen, and then wiped after drying. This was repeated 10 times, and the state of the mark remaining was evaluated according to the following criteria. A: After wiping with a dry cloth, there is no residual trace. B: After wiping with a dry cloth, there is no writing mark left, but there is black residue around it. C: After wiping with a dry cloth, there are a few traces left. D: After wiping with a dry cloth, there are traces of residue.

Claims

1. An active energy ray-curable composition, The active energy ray-curable composition comprises: a compound A and a compound B, The double bond equivalent of the compound A is greater than 200 g / eq, The double bond equivalent of the compound B is 28 g / eq or more and less than 200 g / eq, the double bond equivalent of the active energy ray-curable composition as a whole is less than 365 g / eq, the amount of dissolved oxygen relative to 100% by volume of the dissolved gas is greater than 10% by volume, With respect to the entire active energy ray-curable composition, The iron content is less than 400ppb. The copper atom content is 300 ppb or less.

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

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