Active energy ray-curable composition, cured body and laminate

Abstract

To provide an active energy ray curable composition, a cured product and laminate.SOLUTION: Provided is an active energy ray curable composition, the active energy ray curable composition containing a compound A and a compound B, a double bond equivalent of the compound A is 200 g / eq or more, the double bond equivalent of the compound B is 28 g / eq or more and less than 200 g / eq, the overall double bond equivalent of the active energy ray curable composition is less than 365 g / eq, the amount of dissolved oxygen relative to 100 volume % dissolved gas is more than 10 volume %, and an iron content relative to the whole active energy ray curable composition is 400 ppb or less, and the copper content is 300 ppb 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 technology]

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

[0003] [Patent Document 1] Special Publication No. 62-021815 Summary of the Invention [Problem to be solved by the invention]

[0004] An object of the present invention is to provide an active energy ray-curable composition which can produce a cured product having good curability and stain resistance and which has good stability. [Means for solving the problem]

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

[0006] In the present disclosure, one or more of the above-described features may be provided in further combinations in addition to the combinations explicitly stated. Effect of the Invention

[0007] The active energy ray-curable composition of the present invention has good stability and can produce a cured product having good curability and stain resistance. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0008] Throughout this disclosure, the range of the values ​​of the physical properties, contents, etc. may be set as appropriate (for example, by selecting from the values ​​described in each item below). Specifically, when the value α includes A3, A2, A1 (where A3>A2>A1), the range of the value α may include A3 or less, A2 or less, less than A3, less than A2, A1 or more, A2 or more, greater than A1, greater than A2, A1 to A2 (A1 or more and A2 or less), A1 to A3, A2 to A3, A1 or more and less than A3, A1 or more and less than A2, A2 or more and less than A3, greater than A1 and less than A3, greater than A1 and less than A2, greater than A2 and less than A3, greater than A1 ...2, 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, and the like.

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

[0010] "αβ content (A / B)" means the β content (α) of A relative to 100α of B. α can be, for example, mass %, mol %, or parts by mass. β content can be, for example, the content or amount used. "% by mass content (A / B)" means the content (% by mass) of A relative to 100% by mass of B.

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

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

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

[0014] Examples of the alkyl group include a straight-chain alkyl group, a branched alkyl group, and a cycloalkyl group.

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

[0016] Examples of the branched alkyl group include an i-propyl group, a diethylpentyl group, a trimethylbutyl group, a trimethylpentyl group, and a trimethylhexyl group.

[0017] Examples of the cycloalkyl group include a monocyclic cycloalkyl group, a bridged ring cycloalkyl group, a condensed ring cycloalkyl group, etc. A cycloalkyl group in which at least one hydrogen atom is substituted with an alkyl group is also considered to be a cycloalkyl group.

[0018] "Monocyclic ring" means a ring structure formed by covalent carbon bonds with no internal bridges. "Fused ring" means a ring structure in which two or more monocyclic rings share two atoms in common (i.e., each ring shares only one edge with the other (fused)). "Bridged ring" means a ring structure in which two or more monocyclic rings share three or more atoms in common.

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

[0020] Examples of the bridged ring cycloalkyl group include a tricyclodecyl group, an adamantyl group, and a norbornyl group.

[0021] The alkyl group also includes a group formed by combining a linear alkyl group, a branched alkyl group, and a cycloalkyl group. Examples of the combined group include a cycloalkylalkyl group.

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

[0023] Examples of the alkylene group include a straight-chain alkylene group, a branched alkylene group, and a cycloalkylene group.

[0024] Examples of the straight-chain alkylene group include a methylene group, an ethylene group, a propylene group, an n-butylene group, an n-pentylene group, an n-hexylene group, an n-heptylene group, an n-octylene group, an n-nonylene group, and an n-decamethylene group.

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

[0026] Examples of the cycloalkylene group include a monocyclic cycloalkylene group, a bridged ring cycloalkylene group, a condensed ring cycloalkylene group, etc. In addition, the cycloalkylene group may have one or more hydrogen atoms substituted with a straight-chain or branched alkyl group.

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

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

[0029] Examples of the fused ring cycloalkylene group include a bicyclodecylene group.

[0030] The alkylene group also includes a group formed by combining a linear alkylene group, a branched alkylene group, and a cycloalkylene group, such as a cycloalkylene alkylene group, an alkylenecycloalkylene alkylene group, and the like.

[0031] The cycloalkylene alkylene group is represented by the following formula: -R calkylene -R alkylene - (In the formula, R calkylene R represents a cycloalkylene group. alkylene represents an alkylene group.

[0032] The alkylenecycloalkylenealkylene group is represented by the following formula: -R alkylene -R calkylene -R alkylene - (In the formula, R calkyleneR 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 a phenyl group, a tolyl group, and a mesityl group.

[0036] The fused ring aryl group may, for example, be a naphthyl group.

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

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

[0039] The fused ring arylene group may, for example, be a naphthylene group.

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

[0041] <Compound A: double bond equivalent = 200g / 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 kinds.

[0042] "Double bond equivalent" means the calculated mass per mole of polymerizable double bonds (g / eq).

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

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

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

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

[0047] (Polymer Poly(meth)acrylate) "Polymer poly(meth)acrylate" means a polymer having two or more (meth)acryloyl groups.

[0048] <Double bond-containing site> Examples of the mol % content (double bond-containing portion / polymer (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 (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 mass % to 50 mass %.

[0050] <(Meth)acrylic acid alkyl unit> In one embodiment, the polymer poly(meth)acrylate may contain alkyl (meth)acrylate units. The alkyl (meth)acrylate units may be contained alone or in combination of two or more kinds.

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

[0052] Examples of linear alkyl (meth)acrylates 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-icosyl (meth)acrylate, and n-docosyl (meth)acrylate.

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

[0054] Examples of cycloalkyl (meth)acrylates include cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, cyclopentanyl (meth)acrylate, and isobornyl (meth)acrylate.

[0055] Examples of the molar content (alkyl (meth)acrylate units / polymer poly(meth)acrylate) include 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] Examples of the mass% content ((meth)acrylate alkyl unit / polymer poly(meth)acrylate) are 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] <(Meth)acrylic acid silicone unit> In one embodiment, the polymer poly(meth)acrylate may include a silicone (meth)acrylate unit. The silicone (meth)acrylate unit may be included alone or in combination of two or more kinds.

[0058] In one embodiment, the silicone (meth)acrylate is represented by the following formula: [ka] (In the formula, R AS1 , R AS2 each independently represents a hydrogen atom or a methyl group. AS1 represents an integer of 0 to 6. AS2 represents an integer of 1 to 270.

[0059] Examples of commercially available products ((meth)acrylic silicones) include X-22-2426 (manufactured by Shin-Etsu Silicones), X-22-174D (manufactured by Shin-Etsu Chemical Co., Ltd.), Silaplane FM-0711, FM-0721, and FM-0725 (manufactured by JNC Corporation).

[0060] Examples of the molar content ((meth)acrylic acid silicone unit / polymer poly(meth)acrylate) are 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] Examples of the mass % content ((meth)acrylate alkyl unit / polymer poly(meth)acrylate) are 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)> The production method (polymer poly(meth)acrylate) may be, for example, a method in which an α-functional group-containing polymer is reacted with a β-functional group-containing polymerizable unsaturated compound.

[0063] Examples of combinations (of 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 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] An example of the isocyanate group-containing polymerizable unsaturated compound is 2-isocyanatoethyl (meth)acrylate.

[0068] In one embodiment, the production temperature (for the 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] (double bond-containing silicone) 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 formula: [ka] (In the formula, R S1 ~R S7 R each independently represents a methyl group or a group containing a polymerizable double bond. S8 ~R S11 R each independently represents a methyl group or a phenyl group. S12 represents a substituted methyl group or a substituted phenyl group. S1 represents an integer of 0 or more. S2 represents an integer of 1 or more. S3 represents an integer of 0 or more. However, the compound represented by the above formula has two or more polymerizable double bonds.

[0074] In one embodiment, the double bond-containing silicone is represented by the formula: [ka] (In the formula, R Sa1 ~R Sa3 R each independently represents a methyl group or a group containing a polymerizable double bond. Sa4 represents a substituted methyl group or a substituted phenyl group. S1 represents an integer of 0 or more. S2 represents an integer of 1 or more. S3 represents an integer of 0 or more. However, the compound represented by the above formula has two or more polymerizable double bonds.

[0075] Examples of the polymerizable double bond-containing group include a vinyl group-containing group, a (meth)acryloyl group-containing group, etc. Examples of the polymerizable double bond-containing group include a group in which the following substituent is 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 combinations of these groups.

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

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

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

[0080] In one embodiment, compound A is preferably a silicone chain-containing compound, more preferably a (meth)acrylic acid silicone unit-containing polymer (meth)acrylate, or a double bond-containing silicone, and even more preferably a (meth)acrylic acid dimethylpolysiloxane unit-containing polymer (meth)acrylate, or a double bond-containing dimethylpolysiloxane.

[0081] Examples of the mass% content (compound A / active energy ray curable composition nonvolatile content) include 99 mass%, 95 mass%, 90 mass%, 85 mass%, 80 mass%, 75 mass%, 70 mass%, 65 mass%, 60 mass%, 55 mass%, 50 mass%, 45 mass%, 40 mass%, 35 mass%, 30 mass%, 25 mass%, 20 mass%, 15 mass%, 10 mass%, 5 mass%, 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 100 mass%, more preferably 0.1 mass% to 2 mass%.

[0082] Examples of the mass% content (compound A / active energy ray curable compound) include 99 mass%, 95 mass%, 90 mass%, 85 mass%, 80 mass%, 75 mass%, 70 mass%, 65 mass%, 60 mass%, 55 mass%, 50 mass%, 45 mass%, 40 mass%, 35 mass%, 30 mass%, 25 mass%, 20 mass%, 15 mass%, 10 mass%, 5 mass%, 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 100 mass%, more preferably 0.1 mass% to 2 mass%.

[0083] <Compound B: Double bond equivalent = 28g / eq or more and less than 200g / 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 kinds.

[0084] Examples of compound B include urethane bond-free (poly)(meth)acrylate and urethane (poly)(meth)acrylate.

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

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

[0087] Examples of the (poly)(meth)acrylate 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)glycerin (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. [ka] [In the formula, n is an integer of 0 to 2, and R b1’ ~R b6 ’ each independently represents a hydrogen atom, [ka] In the formula, each q is independently an integer of 0 to 16; 1’ ~R 3’ are each independently a hydrogen atom or an alkyl group, R 1’ may be different groups for each unit. and R b4’ and R b5’may be different groups for each structural unit, Formula (A ’ ) in [ka] In the formula, q is an integer of 0 to 16, and R 1’ ~R 3 ’ are each independently a hydrogen atom or an alkyl group, R 1’ may be different groups for each unit. Contains one or more of.

[0090] In addition, the phrase "the groups may be different for each structural unit" means that, for example, in formula (A'), when n is 2, [ka] R b4A and R b4B may be a group different from R b5A and R b5B This means that the group may be different from the group.

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

[0092] Examples of pentaerythritol (poly)alkylene oxide-modified (meth)acrylates 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 polypentaerythritol (poly)(meth)acrylates 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 polypentaerythritol (poly)alkylene oxide-modified (meth)acrylates 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 side 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 ethylene oxide modified (meth)acrylate, tripentaerythritol 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 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.

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

[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. [ka] [In the formula, m is an integer of 0 to 2, and R b7’ ~R b10 ’ each independently represents a hydrogen atom, [ka] In the formula, each q is independently an integer of 0 to 16; 1’ ~R 3’ are each independently a hydrogen atom or an alkyl group, R 1’may be different groups for each unit. and R b9’ may be different groups for each structural unit, Formula (B ’ ) in [ka] In the formula, q is an integer of 0 to 16, and R 1’ ~R 3 ’ are each independently a hydrogen atom or an alkyl group, R 1’ may be different groups for each unit. Contains one or more of.

[0098] Examples of trimethylolpropane (poly)(meth)acrylates 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), and trimethylolpropane tri(propylene oxide-modified (meth)acrylate).

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

[0101] Examples of polytrimethylolpropane (poly)(meth)acrylates include ditrimethylolpropane (meth)acrylate, ditrimethylolpropane di(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, and ditrimethylolpropane tetra(meth)acrylate.

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

[0103] Examples of polytrimethylolpropane (poly)epoxy modified (meth)acrylates include ditrimethylolpropane epoxy (meth)acrylate, ditrimethylolpropane diepoxy (meth)acrylate, ditrimethylolpropane triepoxy (meth)acrylate, and ditrimethylolpropane tetraepoxy (meth)acrylate.

[0104] <(Poly)glycerin (poly)(alkylene oxide-modified or epoxy-modified) (meth)acrylate> The (poly)glycerin (poly)(alkylene oxide-modified or epoxy-modified) (meth)acrylate is a compound represented by formula (C') or the like. [ka] [In the formula, p is an integer of 0 to 7, and R b11’ ~Rb14 ’ each independently represents a hydrogen atom, [ka] In the formula, q is an integer of 0 to 16, and R 1’ ~R 3’ are each independently a hydrogen atom or an alkyl group, R 1’ may be different groups for each unit. and R b13’ may be different groups for each structural unit, Formula (C ’ ) in [ka] In the formula, q is an integer of 0 to 16, and R 1’ ~R 3 ’ are each independently a hydrogen atom or an alkyl group, R 1’ may be different groups for each unit. Contains one or more of.

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

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

[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 polyglycerol (poly)(meth)acrylates 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 polyglycerin (poly)alkylene oxide-modified (meth)acrylates include diglycerin ethylene oxide-modified (meth)acrylate, diglycerin di(ethylene oxide-modified (meth)acrylate), diglycerin tri(ethylene oxide-modified (meth)acrylate), diglycerin tetra(ethylene oxide-modified (meth)acrylate), triglycerin 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 propylene 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 propylene oxide modified (meth)acrylate, triglycerin di(propylene oxide modified (meth)acrylate), triglycerin tri(propylene oxide modified (meth)acrylate), triglycerin tetra(propylene oxide modified (meth)acrylate), triglycerin penta(propylene oxide modified (meth)acrylate), and the like.

[0110] Examples of polyglycerol (poly)epoxy modified (meth)acrylates 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] <Isocyanurate structure-containing (poly)(alkylene oxide-modified or epoxy-modified) (meth)acrylate> The isocyanurate structure-containing (poly)(alkylene oxide-modified or epoxy-modified) (meth)acrylate is a compound represented by formula (D') or the like. [ka] [In the formula, R b15’ ~R b17 ’ each independently represents a hydrogen atom, [ka] In the formula, q is an integer of 0 to 16, and R 1’ ~R 3’ are each independently a hydrogen atom or an alkyl group, R 1’ may be different groups for each unit. and the formula (D ’ ) in [ka] In the formula, q is an integer of 0 to 16, and R 1’ ~R 3 ’ are each independently a hydrogen atom or an alkyl group, R 1’ may be different groups for each unit. Contains one or more of.

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

[0113] Examples of the isocyanurate structure-containing (poly)alkylene oxide-modified (meth)acrylate 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 isocyanurate structure-containing (poly)epoxy-modified (meth)acrylate 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> The (poly)alkylene (poly)(alkylene oxide-modified or epoxy-modified) (meth)acrylate is a compound represented by the formula (E') or the like. [ka] [In the formula, R b18’ ~R b19 ’ each independently represents a hydrogen atom, [ka] In the formula, q is an integer of 0 to 16, and R 1’ ~R 3 ’ are each independently a hydrogen atom or an alkyl group, R 1’ may be different groups for each unit. and R b20’ is an alkylene group, r is an integer of 1 or more, Formula (E ’ ) in [ka] In the formula, q is an integer of 0 to 16, and R 1’ ~R 3 ’ are each independently a hydrogen atom or an alkyl group, R 1’ may be different groups for each unit. Contains one or more of.

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

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

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

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

[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 polyalkylene glycol dialkylene oxide-modified (meth)acrylates include diethylene glycol di(ethylene oxide-modified (meth)acrylate), dipropylene glycol di(ethylene oxide-modified (meth)acrylate), triethylene glycol (ethylene oxide-modified (meth)acrylate), and tripropylene glycol (ethylene oxide-modified (meth)acrylate).

[0122] Examples of polyalkylene glycol diepoxy modified (meth)acrylates 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. [ka] [In the formula, R b21’ ~R b22 ’ are each independently [ka] In the formula, q is an integer of 0 to 16, and R 1’ ~R 3 ’ are each independently a hydrogen atom or an alkyl group, R 1’ may be different groups for each unit. and the formula (F ’ ) in [ka] In the formula, q is an integer of 0 to 16, and R 1’ ~R 3 ’ are each independently a hydrogen atom or an alkyl group, R 1’ may be different groups for each unit. Contains one or more of.

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

[0125] Examples of bisphenol A (poly)alkylene oxide-modified (meth)acrylates 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 reaction products of a compound group containing a hydroxyl group-containing (poly)(meth)acrylate and a polyisocyanate.

[0129] <Hydroxyl group-containing (poly)(meth)acrylate> Examples of hydroxyl group-containing (poly)(meth)acrylates include hydroxyl group-containing (poly)pentaerythritol (poly)(meth)acrylate, hydroxyl group-containing (poly)trimethylolpropane (poly)(meth)acrylate, and hydroxyl group-containing (poly)glycerin (poly)(meth)acrylate.

[0130] The polyisocyanates may be used alone or in combination of two or more.

[0131] <Polyisocyanate> "Polyisocyanate" means a compound that has two or more isocyanate groups (-N=C=O).

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

[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 polyisocyanates, crosslinked cyclic alicyclic polyisocyanates, and condensed cyclic alicyclic polyisocyanates.

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

[0138] An example of the condensed ring alicyclic polyisocyanate is bicyclodecylene diisocyanate.

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

[0140] Examples of monocyclic aromatic polyisocyanates include 4,4'-diphenyldimethylmethane diisocyanate, 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.

[0141] The condensed ring aromatic polyisocyanate may, for example, be 1,5-naphthylene diisocyanate.

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

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

[0144] Examples of the mass% content (compound B / active energy ray curable compound) include 90 mass%, 85 mass%, 81 mass%, 80 mass%, 78 mass%, 75 mass%, 70 mass%, 69 mass%, 68 mass%, 65 mass%, 60 mass%, 55 mass%, 50 mass%, 45 mass%, 40 mass%, 35 mass%, 30 mass%, 25 mass%, 20 mass%, 15 mass%, 10 mass%, 5 mass%, 0 mass%, etc. In one embodiment, the content is preferably 0 mass% to 90 mass%.

[0145] <Double bond equivalent (whole active energy ray-curable composition)> Examples of the double bond equivalent (whole active energy ray-curable composition) include 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, 86 g / eq, 85 g / eq, 75 g / eq, 50 g / eq, and 28 g / eq. 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, even more preferably 85 g / eq to 360 g / eq, and particularly preferably 90 g / eq to 125 g / eq.

[0146] The double bond equivalent (whole 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 (whole 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 value=A×(α / 100)+B×(β / 100)

[0147] <Amount of dissolved oxygen relative to 100% by volume of dissolved gas: Amount of dissolved oxygen> The amount of dissolved oxygen relative to 100% by volume of dissolved gas in the active energy ray-curable composition may be, 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 more than 10% by volume. In one embodiment, the amount of dissolved oxygen is preferably more than 10% by volume, more preferably more than 10% by volume and less than 20% by volume, and even more preferably 13% by volume 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 (Mettler Toledo Co., Ltd.) Converter: M400 (Mettler Toledo) Measurement temperature: normal temperature (20℃~25℃)

[0149] The amount of dissolved oxygen can be adjusted by a method such as bubbling air into the composition.

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

[0152] The iron atom and the copper atom may be present in the active energy ray-curable composition in various forms, such as a zero-valent metal or an ion.

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

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

[0155] The iron atom content and copper atom content can be measured by the following method. Analysis type: ICP-MS Equipment manufacturer: PerkinElmer Device name: ELAN DRCII Measurement pretreatment: Dilute with 1% nitric acid NMP (N-methyl-2-pyrrolidone) Quantitative method: Absolute quantitation using a calibration curve method with a standard sample Standard sample concentrations for calibration curve: 0ppb, 1ppb, 2ppb, 5ppb, 20ppb, 50ppb Sample concentration: 0.5% (200-fold dilution)

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

[0157] Examples of the photopolymerization initiator include an α-hydroxydimethylacetophenone group-containing photopolymerization initiator, α-hydroxycycloalkylphenone, α-aminoalkylphenone, benzyl dimethyl ketal, unsubstituted or substituted alkylphenone, unsubstituted or substituted benzyl, unsubstituted or substituted benzophenone, acylphosphine oxide, substituted thioxanthone, and oxime ester.

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

[0159] Examples of α-hydroxycycloalkylphenones include 1-hydroxycyclohexyl phenyl ketone.

[0160] Examples of α-aminoalkylphenones include 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one.

[0161] An example of the benzyl dimethyl ketal is 2,2-dimethoxy-1,2-diphenylethan-1-one.

[0162] Examples of unsubstituted or substituted alkylphenones include benzoin methyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin ethyl ether, acetophenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2-phenyl-2-(p-toluenesulfonyloxy)acetophenone, benzoin, 2-benzyl-2-(dimethylamino)-4'-morpholinobutyrophenone, 2-methyl-4'-(methylthio)-2-morpholinopropiophenone, 2-isonitrosopropiophenone, and 2,2-dimethoxy-1,2-diphenylethan-1-one.

[0163] Examples of unsubstituted or substituted benzyl include benzyl and p-anisyl.

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

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

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

[0167] Oxime esters include, for example, 1,2-octanedione, 1-[4-(phenylthio)-, 2-(O-benzoyloxime)] (i.e., 2-((benzoyloxy)imino)-1-(4-(phenylthio)phenyl)octan-1-one); Examples include ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime) (i.e., 1-(((1-(9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl)ethylidene)amino)oxy)ethan-1-one).

[0168] When electron beam curing is used, a photoinitiator is not necessary.

[0169] In one embodiment, the photopolymerization initiator preferably includes an α-aminoalkylphenone, and more preferably includes 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one.

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

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

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

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

[0174] Examples of aromatic solvents include toluene and xylene.

[0175] Examples of the alcohol solvent include methanol, ethanol, n-propanol, isopropanol, n-butanol, i-butanol, and t-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 glycol ether solvents include ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol monoisopropyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol monoisobutyl ether, and ethylene glycol mono-t-butyl ether.

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

[0180] The haloalkane solvent may, for example, be chloroform.

[0181] The amide solvent may, for example, be dimethylformamide.

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

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

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

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

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

[0187] In one embodiment, the part by mass content (additive / compound A), the part by mass content (additive / compound B), the part by mass content (additive / photopolymerization initiator), and the part by mass content (additive / organic solvent) are preferably less than 5 parts by mass, less than 1 part by mass, less than 0.1 parts by mass, less than 0.01 parts by mass, 0 parts by mass, etc.

[0188] By dispersing and mixing the above-mentioned agents, an active energy ray-curable composition can be produced.

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

[0190] Examples of uses (of the active energy ray-curable composition) include coating agents, hard coating agents, clear coating agents, clear hard coating agents, anti-glare coating agents, anti-glare hard coating agents, coating agents for optical films, hard coating agents for optical films, release coating agents, release film coating agents, and undercoating agents.

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

[0192] The curing conditions are, for example, as follows:

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

[0194] The production method (laminate) may be, for example, a method including the following steps. Active energy ray curable composition coating step: a step of coating an active energy ray curable composition on at least one surface of a substrate. Active energy ray curing step: a step of forming a cured layer of an active energy ray curable composition by irradiating with active energy rays

[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 (base material) is preferably 10 μm to 2000 μm.

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

[0198] (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 coat coating, offset printing, flexographic printing, and screen printing.

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

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

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

[0202] When an electron beam is used, the curing conditions are preferably as follows: Acceleration voltage: 10kV~300kV Conveying speed: 5m / min to 50m / min EXAMPLES

[0203] The present invention will be specifically described below through examples and comparative examples. However, the above description and the following examples are not intended to limit the present invention. The present invention is limited only by the claims. Unless otherwise specified below, numerical values ​​such as parts and % are based on mass.

[0204] Production Example 1 Polymer (meth)acrylate A four-neck flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen inlet was charged with 125 parts of butyl acetate, 100 parts of glycidyl methacrylate (GMA), and 1 part of azobisisobutyronitrile (AIBN), and stirred. The mixture was heated to 100°C under a nitrogen stream and reacted for 10 hours. After the reaction was completed, the mixture was cooled to 60°C, and 25 parts of acrylic acid (AA), 0.1 parts of triphenylphosphine, and 0.05 parts of methoquinone were charged. The nitrogen inlet was replaced with an air bubbling device, and the mixture was stirred while bubbling air into the reaction solution. The mixture was heated to 110°C and reacted for 9 hours while keeping the temperature constant, to obtain a polymer (meth)acrylate (non-volatile content 50%). Into a four-neck flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen inlet, 48.6 parts of butyl acetate, 32.6 parts of glycidyl methacrylate (hereinafter, GMA), and The mixture was stirred and heated to 100°C under nitrogen flow, and reacted for 10 hours. After the reaction was completed, the mixture was cooled to 60°C, and 16.6 parts of acrylic acid, 0.1 parts of triphenylphosphine, and 0.5 parts of methoquinone were added. The nitrogen inlet was replaced with an air bubbling device, and the mixture was stirred while bubbling air into the reaction solution. The mixture was heated to 110°C and reacted for 9 hours while keeping the temperature constant, to obtain Resin 1 with a resin solid content of 50% (Table 1). The weight average molecular weight (polystyrene equivalent value by GPC) was 12,000, and the molecular weight per acrylic group was calculated to be 214. The weight average molecular weight was measured by gel permeation chromatography (Tosoh Corporation, product name "HLC-8220", column: Tosoh Corporation, product name "TSKgel superHZ2000" three columns connected in series.

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

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

[0207] Example 1 Active energy ray-curable composition The substances shown in the table below were mixed as non-volatile components, and then diluted with a mixed solvent of isopropyl alcohol / methyl ethyl ketone = 70% / 30% (non-volatile content 40%). Next, the obtained active energy ray curable composition was filtered using a Zeta Plus activated carbon adsorption depth filter cartridge R53S (manufactured by 3M). The amount of dissolved oxygen was adjusted by bubbling air into the composition. The iron atom content and copper atom content were adjusted by adding an iron salt or a copper salt after filtration, as necessary.

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

[0209] [Table 2] [Table 3] [Table 4] [Table 5] The numerical values ​​for compounds A and B are values ​​(%) relative to 100% by mass of the double bond-containing compound. The numerical value of the initiator is the value relative to 100 parts by mass of the double bond-containing compound. Compound A [ka] Gly3A: Glycerin triacrylate: Product name "Aronix M-930", manufactured by Toagosei Co., Ltd. DPPA: Dipentaerythritol polyacrylate, product name "NK Ester A-9550", manufactured by Shin-Nakamura Chemical Co., Ltd. DPEA-12: Ethylene oxide modified dipentaerythritol hexaacrylate, product name "KAYARAD DPEA-12", manufactured by Nippon Kayaku Co., Ltd. Omnirad 907: 2-Methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, IGM Resins Omnirad 184: 1-Hydroxycyclohexyl phenyl ketone, IGM Resins Omnirad TPO H: 2,4,6-trimethylbenzoyldiphenylphosphine oxide, IGM Resins Omnirad 1173: 2-hydroxy-2-methyl-1-phenylpropanone, IGM Resins

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

[0211] The iron atom and copper atom contents were measured by the following method. Analysis type: ICP-MS Equipment manufacturer: PerkinElmer Device name: ELAN DRCII Measurement pretreatment: Dilute with 1% nitric acid NMP (N-methyl-2-pyrrolidone) Quantitative method: Absolute quantitation using a calibration curve method with a standard sample Standard sample concentrations for calibration curve: 0ppb, 1ppb, 2ppb, 5ppb, 20ppb, 50ppb Sample concentration: 0.5% (200-fold dilution)

[0212] (stability) The active energy ray-curable composition was stored at 20° C., and the number of days until gelation was measured. A: It does not gel even after 6 months. B: Gelation occurs between 5 months and 6 months. C: Gelling occurs between 4 months and 5 months. D: Gelled within 4 months.

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

[0214] (curable) A cotton swab soaked in methyl ethyl ketone was rubbed back and forth against the surface of the cured product, and the cured product was visually observed and evaluated according to the following criteria. A: Even after 20 strokes, no change was observed in the cured product. B: After 20 strokes, whitening was observed on the cured product. C: After 10 strokes, whitening was observed on the cured product. D: After 5 strokes, whitening is observed on the cured product.

[0215] (Stain resistance) The surface of the cured product was written on with an oil-based marker, dried, and then wiped off 10 times. The state of remaining marks was evaluated according to the following criteria. A: After wiping with a dry cloth, no traces remain. B: After wiping with a dry cloth, no traces remain, but the surrounding area remains black. C: After wiping with a dry cloth, slight marks remain. D: After wiping with a dry cloth, there are traces remaining.

Claims

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

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

3. A laminate comprising the cured product according to claim 2.

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