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

Abstract

The active energy ray-curable composition comprises a low molecular anionic emulsifier, a high molecular anionic emulsifier, poly (meth) acrylate and water, the weight average molecular weight of the low molecular anionic emulsifier is less than 10,000, and the weight average molecular weight of the high molecular anionic emulsifier is 10,000-150,000.

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 developed to impart functionality to the surfaces of various substrates. In recent years, there has been a demand for aqueous active energy ray-curable compositions from the perspective of global environmental protection.

[0003] [Prior art literature]

[0004] [Patent Document]

[0005] Patent Document 1: Japanese Patent Application Laid-Open No. 2008-303258 Summary of the Invention

[0006] [Problems to be solved by the invention]

[0007] The problem to be solved by the present invention is to provide an active energy ray-curable composition having good emulsification, mechanical stability and high-temperature stability.

[0008] [Technical means to solve the problem]

[0009] According to the present disclosure, the following items are provided.

[0010] (Item 1)

[0011] An active energy ray-hardening composition,

[0012] The active energy ray-curable composition comprises a low molecular weight anionic emulsifier, a high molecular weight anionic emulsifier, a poly(meth)acrylate, and water.

[0013] The weight average molecular weight of the low molecular anionic emulsifier is less than 10,000.

[0014] The weight average molecular weight of the polymer anionic emulsifier is 10,000 to 150,000.

[0015] (Item 2)

[0016] According to the active energy ray-curable composition described in the above item, the low-molecular-weight anionic emulsifier is polyoxyalkylenesulfonate ammonium (meth)acrylate.

[0017] (Item 3)

[0018] A cured product comprising the active energy ray-curable composition according to any one of the above items.

[0019] (Item 4)

[0020] A laminate comprising the hardened article according to the above item.

[0021] In the present disclosure, one or more features may be provided in further combinations other than the explicit combinations.

[0022] [Effects of the Invention]

[0023] The active energy ray-curable composition disclosed herein has good emulsification, mechanical stability, and high-temperature stability. DETAILED DESCRIPTION

[0024] Throughout the present disclosure, the ranges of the values ​​of various physical property values, contents, etc. can be set as appropriate (for example, selected from the values ​​described in the following items). Specifically, regarding the value α, when A3, A2, A1 (assuming A3>A2>A1) and the like are listed, the range of the value α is listed as follows: A3 or less, A2 or less, less than A3, less than A2, A1 or more, A2 or more, greater than A1, greater than A2, A1 to A2 (A1 or more and A2 or less), A1 to A3, A2 to A3, A1 or more and less than A3, A1 or more and less than A2, A2 or more and less than A3, greater than A1 and less than A3, greater than A1 and less than A2, greater than A2 and less than A3, greater than A1 and A3, greater than A1 and less than A2, greater than A2 and less than A3, greater than A1 and A3 or less, greater than A1 and A2 or less, greater than A2 and A3 or less, and the like.

[0025] As long as the problems to be solved by the present invention are solved, the components, conditions, numerical values, etc. are not particularly limited.

[0026] "αβ amount (A / B)" refers to the β amount (α) of A relative to 100α of B. Examples of α include mass %, mole %, and parts by mass. Examples of β amount include content and usage amount. "Mass % content (A / B)" refers to the content (mass %) of A relative to 100% of B.

[0027] "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.

[0028] 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 until a constant weight is achieved.

[0029] “(Meth)acrylic acid” means “acrylic acid and / or methacrylic acid.” “(Meth)acrylate” means “acrylate and / or methacrylate.” “(Meth)acryloyl” means “acryloyl and / or methacryloyl.”

[0030] "(Meth)allyl" means "allyl and / or methallyl".

[0031] "C..." means "having a carbon number..." For example, "C1-C6 alkyl" means an alkyl group having 1 to 6 carbon atoms. "C6 alkyl" means an alkyl group having 6 carbon atoms.

[0032] Examples of the alkyl group include a linear alkyl group, a branched alkyl group, and a cycloalkyl group.

[0033] 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.

[0034] The "branched alkyl group" refers to a group in which at least one hydrogen atom of a linear alkyl group is substituted with an alkyl group and the group does not have a cyclic structure.

[0035] Examples of the branched alkyl group include isopropyl, diethylpentyl, trimethylbutyl, trimethylpentyl, and trimethylhexyl.

[0036] Examples of the cycloalkyl group include a monocyclic cycloalkyl group, a cross-linked cycloalkyl group, a condensed cycloalkyl group, etc. Furthermore, a cycloalkyl group in which at least one hydrogen atom is substituted by an alkyl group is also considered to be a cycloalkyl group.

[0037] "Monocyclic ring" refers to a ring structure formed by covalent bonds of carbon atoms without an internal bridge structure. "Fused ring" refers to a ring structure in which two or more monocyclic rings share two atoms (i.e., they only share (fuse) one edge of each ring). "Cross-linked ring" refers to a ring structure in which two or more monocyclic rings share three or more atoms.

[0038] Examples of the monocyclic cycloalkyl group include cyclopentyl, cyclohexyl, cycloheptyl, cyclodecyl, and 3,5,5-trimethylcyclohexyl.

[0039] Examples of the cross-linked cycloalkyl group include tricyclodecanyl, adamantyl, and norbornyl.

[0040] Furthermore, the alkyl group also includes a combination of a straight-chain alkyl group, a branched alkyl group, and a cycloalkyl group. Examples of such a combination include a cycloalkylalkyl group and the like.

[0041] The cycloalkylalkyl group is represented by the following formula.

[0042] R calkyl -R alkyl -

[0043] (where R calkyl Represents a cycloalkyl group. alkyl represents an alkyl group.)

[0044] Examples of the alkylene group include a linear alkylene group, a branched alkylene group, and a cycloalkylene group.

[0045] Examples of the linear alkylene group include methylene, ethylene, propylene, n-butylene, n-pentylene, n-hexylene, n-heptylene, n-octylene, n-nonylene, and n-decamethylene.

[0046] Examples of the branched alkylene group include diethylpentylene, trimethylbutylene, trimethylpentylene, and trimethylhexylene.

[0047] Examples of the cycloalkylene group include monocyclic cycloalkylene groups, cross-linked cycloalkylene groups, and condensed cycloalkylene groups. In addition, one or more hydrogen atoms of the cycloalkylene group may be substituted with a linear or branched alkyl group.

[0048] Examples of the monocyclic cycloalkylene group include cyclopentylene, cyclohexylene, cycloheptylene, cyclodecylene, and 3,5,5-trimethylcyclohexylene.

[0049] Examples of the cross-linked cycloalkylene group include tricyclodecanylene, adamantylene, and norbornylene.

[0050] Examples of the fused ring cycloalkylene group include biscyclodecylene and the like.

[0051] Furthermore, the alkylene group also includes a combination of a linear alkylene group, a branched alkylene group, and a cycloalkylene group. Examples of such a combination include cycloalkylenealkylene groups and alkylenecycloalkylenealkylene groups.

[0052] The cycloalkylenealkylene group is represented by the following formula.

[0053] -R calkylene -R alkylene -

[0054] (where R calkylene Represents a cycloalkylene group. alkylene represents an alkylene group.)

[0055] The alkylenecycloalkylenealkylene group is represented by the following formula.

[0056] -R alkylene -R calkylene -R alkylene -

[0057] (where R calkylene Represents a cycloalkylene group. alkylene represents an alkylene group.)

[0058] 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.

[0059] Examples of the aryl group include a monocyclic aryl group and a condensed ring aryl group.

[0060] Examples of the monocyclic aryl group include phenyl, tolyl, and mesityl.

[0061] Examples of the fused ring aryl group include naphthyl and the like.

[0062] Examples of the arylene group include a monocyclic arylene group and a condensed ring arylene group.

[0063] Examples of the monocyclic arylene group include a phenylene group and a tolylene group.

[0064] Examples of the fused ring arylene group include naphthylene and the like.

[0065] [Active energy ray-curable composition]

[0066] The present disclosure relates to an active energy ray-hardenable composition.

[0067] The active energy ray-curable composition comprises a low molecular weight anionic emulsifier, a high molecular weight anionic emulsifier, a poly(meth)acrylate, and water.

[0068] The weight average molecular weight of the low molecular anionic emulsifier is less than 10,000.

[0069] The weight average molecular weight of the polymer anionic emulsifier is 10,000 to 150,000.

[0070] <Low molecular weight anionic emulsifier>

[0071] The low-molecular anionic emulsifiers may be used alone or in combination of two or more.

[0072] Examples of anionic groups include sulfate groups (-OSO3X), sulfonate groups (-SO3X), phosphate groups (-OPO(OX)2), phosphonate groups (-PO(OX)2), carboxylate groups (-COOX), borate groups (-B(OX)2) (X = cationic group), etc.

[0073] Examples of the low-molecular-weight anionic emulsifier include reactive low-molecular-weight anionic emulsifiers and non-reactive low-molecular-weight anionic emulsifiers.

[0074] (Reactive low molecular weight anionic emulsifier)

[0075] The reactive low-molecular anionic emulsifiers may be used alone or in combination of two or more.

[0076] Examples of the reactive group include a (meth)acryloyl group and a (meth)allyl group.

[0077] Examples of the reactive low-molecular-weight anionic emulsifier include polyoxyalkylenesulfonate ammonium (meth)acrylate and the like.

[0078] Examples of the polyoxyalkylenesulfonate ammonium (meth)acrylate include polyoxyalkylene polyarylethersulfonate ammonium (meth)acrylate.

[0079] In one embodiment, polyoxyalkylenesulfonate ammonium (meth)acrylate is represented by the following formula.

[0080] [Chemistry 1]

[0081]

[0082] [Where R 1 ~R 5 R each independently represents a hydrogen atom, an alkyl group or an arylalkyl group. 1 ~R 5 May be different.

[0083] R 6 represents a C2 to C4 alkylene group. n represents an integer from 5 to 150. In each structural unit, R 6 May be different.

[0084] R 7 R each independently represents a hydrogen atom or a C1-C10 hydrocarbon group. 8 R represents an alkylene group. 9 represents a hydrogen atom or a methyl group.]

[0085] Examples of the arylalkyl group include 1-phenylethyl and the like.

[0086] In one embodiment, in the formula, R 1 and R 5 represents a hydrogen atom, R 2 and R 4 represents 1-phenylethyl, R 3 Represents a methyl group.

[0087] (Non-reactive low molecular weight anionic emulsifier)

[0088] The non-reactive low-molecular anionic emulsifiers may be used alone or in combination of two or more.

[0089] Examples of the non-reactive low-molecular anionic emulsifier include non-reactive low-molecular carboxylic acid emulsifiers, non-reactive low-molecular sulfate emulsifiers, non-reactive low-molecular sulfonate emulsifiers, and non-reactive low-molecular phosphate emulsifiers.

[0090] Examples of the non-reactive low-molecular carboxylic acid emulsifier include rosin acid salts, fatty acid salts, and acylated sarcosinates.

[0091] Examples of the non-reactive low molecular weight sulfate emulsifier include alkyl sulfate salts, alkyl ether sulfate salts, amide ether sulfates, polyoxyalkylene alkyl ether sulfate salts, polyoxyalkylene dialkyl ether sulfate salts, polyoxyalkylene trialkyl ether sulfate salts, and polyoxyalkylene alkyl aryl ether sulfate salts.

[0092] Examples of the non-reactive low molecular weight sulfonate emulsifier include polyoxyalkylene alkyl sulfosuccinates, sulfosuccinic acid diester salts, sulfosuccinate ester salts, and dialkyl sulfosuccinate ester salts.

[0093] Examples of the non-reactive low molecular weight phosphate emulsifier include alkyl phosphates and alkyl ether phosphates.

[0094] In one embodiment, the low molecular weight anionic emulsifier is preferably polyoxyalkylenesulfonate ammonium (meth)acrylate. The reason for this preference is, for example, that the scratch resistance and wet heat resistance of the cured product are improved.

[0095] In one embodiment, the low molecular weight anionic emulsifier is preferably polyoxyalkylenesulfonate ammonium (meth)acrylate. The reason for this preference is, for example, that the scratch resistance and wet heat resistance of the cured product are improved.

[0096] Examples of the weight average molecular weight (low molecular weight anionic emulsifier) ​​include less than 10,000, 9999, 9500, 9000, 8500, 8000, 7500, 7000, 6500, 6000, 5500, 5000, 4500, 4000, 3500, 3000, 2500, 2000, 1900, 1800, 1700, 1600, 1500, 1400, 1300, 1200, 1100, 1000, 500, 300, 250, and 100. In one embodiment, the weight average molecular weight is preferably less than 10,000, more preferably 100 or more and less than 10,000, further preferably 300 or more and less than 10,000, and particularly preferably 300 to 2000.

[0097] The weight average molecular weight and number average molecular weight can be determined according to the following conditions.

[0098] Measuring instrument: GPC (model: HLC-8220) manufactured by Tosoh Co., Ltd.

[0099] Column: Tosoh Corporation's guard column, TSK gel guard column α (1 column) and TSK-GEL α-M (2 columns) (temperature 40°C)

[0100] Detector: TDA Model 301 manufactured by VISCOTECH (concentration detector, 90° light scattering detector, and viscosity detector (temperature 40°C)) RALLS method

[0101] Eluent: 0.02M NaNO3 / CH3CN=80 / 20wt%

[0102] Sample concentration: 0.5wt%

[0103] Development temperature: 40℃

[0104] Standard substance: polyethylene oxide

[0105] Flow rate: 1.0 mL / min

[0106] Measurement Sample: First, prepare the measurement sample by adding the eluent to a non-volatile concentration of 0.5%. Next, add sodium hydroxide aqueous solution until the pH reaches 10-12. Then, immerse in a hot water bath at 80°C or higher for 1 hour. Then, adjust the pH to 6-8 with sulfuric acid and dilute to 0.025% with the eluent before measurement.

[0107] Examples of the mass % content (low-molecular-weight anionic emulsifier / active energy ray-curable composition non-volatile component) include 20 mass %, 19 mass %, 17 mass %, 15 mass %, 13 mass %, 11 mass %, 10 mass %, 9 mass %, 7 mass %, 5 mass %, 3 mass %, 2 mass %, 1.5 mass %, 1 mass %, 0.9 mass %, 0.7 mass %, 0.5 mass %, 0.3 mass %, 0.1 mass %, 0.09 mass %, 0.07 mass %, 0.05 mass %, 0.03 mass %, and 0.01 mass %. In one embodiment, the content is preferably 0.01 mass % to 20 mass %, and more preferably 0.05 mass % to 10 mass %. This is preferred because, for example, water resistance is improved.

[0108] <Polymer anionic emulsifier>

[0109] The polymer anionic emulsifiers may be used alone or in combination of two or more.

[0110] Examples of the high molecular weight anionic emulsifier include polymers containing anionic group-containing monomer units and hydrophobic monomer units.

[0111] (Anionic group-containing monomer)

[0112] The anionic group-containing monomers may be used alone or in combination of two or more.

[0113] Examples of the anionic group-containing monomer include a carboxyl group-containing monomer, a sulfonic acid group-containing monomer, a phosphoric acid group-containing monomer, and salts thereof.

[0114] Examples of the mass % content (anionic group-containing monomer units / polymer anionic emulsifier) ​​include 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 %, and 5 mass %. In one embodiment, the content is preferably 5 to 95 mass %.

[0115] Examples of the mol% content (anionic group-containing monomer units / polymer anionic emulsifier) ​​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%, and 5 mol%. In one embodiment, the content is preferably 5 mol% to 95 mol%.

[0116] Examples of the salt include inorganic salts and organic salts.

[0117] Examples of the inorganic salt include lithium salt, sodium salt, potassium salt, and calcium salt.

[0118] Examples of the organic salt include ammonium salts and amine salts.

[0119] Carboxyl-containing monomers

[0120] The carboxyl group-containing monomers may be used alone or in combination of two or more.

[0121] Examples of the carboxyl group-containing monomer include monomers having one carboxyl group and monomers having multiple carboxyl groups.

[0122] The mass % content (carboxyl group-containing monomeric unit / polymer anionic emulsifier) ​​includes, for example, 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 %, 0.5 mass %, 0.1 mass %, 0.05 mass %, 0.01 mass %, 0 mass %, etc. In one embodiment, the content preferably includes 0 mass % to 95 mass %.

[0123] The mol% content (carboxyl group-containing monomer unit / polymer anionic emulsifier) ​​includes, for example, 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%, 4 mol%, 2 mol%, 1 mol%, 0.5 mol%, 0.1 mol%, 0.05 mol%, 0.01 mol%, 0 mol%, etc. In one embodiment, the content is preferably 0 mol% to 95 mol%.

[0124] Examples of the monomer having one carboxyl group include (meth)acrylic acid and crotonic acid.

[0125] Examples of the mass % content (monomer unit having one carboxyl group / polymer anionic emulsifier) ​​include 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 %, 0.5 mass %, 0.1 mass %, 0.05 mass %, 0.01 mass %, and 0 mass %. In one embodiment, the content is preferably 0 to 95 mass %.

[0126] Examples of the mol% content (monomer unit having one carboxyl group / polymer anionic emulsifier) ​​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%, 4 mol%, 2 mol%, 1 mol%, 0.5 mol%, 0.1 mol%, 0.05 mol%, 0.01 mol%, and 0 mol%. In one embodiment, the content is preferably 0 to 95 mol%.

[0127] Examples of the monomer having a plurality of carboxyl groups include maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, and anhydrous citraconic acid.

[0128] Examples of the mass % content (monomer units having multiple carboxyl groups / polymer anionic emulsifier) ​​include 20 mass %, 15 mass %, 10 mass %, 9 mass %, 8 mass %, 7 mass %, 6 mass %, 5 mass %, 4 mass %, 3 mass %, 2 mass %, 1 mass %, 0.5 mass %, 0.1 mass %, 0.05 mass %, 0.01 mass %, and 0 mass %. In one embodiment, the content is preferably 0 to 20 mass %.

[0129] The mol% content (monomer units having multiple carboxyl groups / polymer anionic emulsifier) ​​includes 20 mol%, 15 mol%, 10 mol%, 9 mol%, 8 mol%, 7 mol%, 6 mol%, 5 mol%, 4 mol%, 3 mol%, 2 mol%, 1 mol%, 0.5 mol%, 0.1 mol%, 0.05 mol%, 0.01 mol%, 0 mol%, etc. In one embodiment, the content is preferably 0 mol% to 20 mol%.

[0130] Sulfonic acid group-containing monomers

[0131] The sulfonic acid group-containing monomers may be used alone or in combination of two or more.

[0132] Examples of the sulfonic acid group-containing monomer include sulfonic acid group-containing aliphatic hydrocarbon monomers, sulfonic acid group-containing aromatic hydrocarbon monomers, and sulfonic acid group-containing non-hydrocarbon monomers.

[0133] Examples of the mass % content (sulfonic acid group-containing monomer units / polymer anionic emulsifier) ​​include 15 mass %, 10 mass %, 9 mass %, 8 mass %, 7 mass %, 6 mass %, 5 mass %, 4 mass %, 3 mass %, 2 mass %, 1 mass %, 0.5 mass %, 0.1 mass %, 0.05 mass %, 0.01 mass %, and 0 mass %. In one embodiment, the content is preferably 0 mass % to 15 mass %.

[0134] The mole % content (sulfonic acid group-containing monomer unit / polymer anionic emulsifier) ​​includes 15 mol%, 10 mol%, 9 mol%, 8 mol%, 7 mol%, 6 mol%, 5 mol%, 4 mol%, 3 mol%, 2 mol%, 1 mol%, 0.5 mol%, 0.1 mol%, 0.05 mol%, 0.01 mol%, 0 mol%, etc. In one embodiment, the content is preferably 0 mol% to 15 mol%.

[0135] Examples of the sulfonic acid group-containing aliphatic hydrocarbon monomer include (meth)allylsulfonic acid.

[0136] Examples of the mass % content (sulfonic acid group-containing aliphatic hydrocarbon monomer unit / polymer anionic emulsifier) ​​include 15 mass %, 10 mass %, 9 mass %, 8 mass %, 7 mass %, 6 mass %, 5 mass %, 4 mass %, 3 mass %, 2 mass %, 1 mass %, 0.5 mass %, 0.1 mass %, 0.05 mass %, 0.01 mass %, and 0 mass %. In one embodiment, the content is preferably 0 mass % to 15 mass %.

[0137] The mole % content (sulfonic acid group-containing aliphatic hydrocarbon monomer unit / polymer anionic emulsifier) ​​includes 15 mol%, 10 mol%, 9 mol%, 8 mol%, 7 mol%, 6 mol%, 5 mol%, 4 mol%, 3 mol%, 2 mol%, 1 mol%, 0.5 mol%, 0.1 mol%, 0.05 mol%, 0.01 mol%, 0 mol%, etc. In one embodiment, the content is preferably 0 mol% to 15 mol%.

[0138] Examples of the sulfonic acid group-containing aromatic hydrocarbon monomer include styrenesulfonic acid, vinylsulfonic acid, and 2-sulfoethyl (meth)acrylate.

[0139] Examples of the mass % content (sulfonic acid group-containing aromatic hydrocarbon monomer unit / polymer anionic emulsifier) ​​include 15 mass %, 10 mass %, 9 mass %, 8 mass %, 7 mass %, 6 mass %, 5 mass %, 4 mass %, 3 mass %, 2 mass %, 1 mass %, 0.5 mass %, 0.1 mass %, 0.05 mass %, 0.01 mass %, and 0 mass %. In one embodiment, the content is preferably 0 mass % to 15 mass %.

[0140] The mole % content (sulfonic acid group-containing aromatic hydrocarbon monomer unit / polymer anionic emulsifier) ​​includes 15 mol%, 10 mol%, 9 mol%, 8 mol%, 7 mol%, 6 mol%, 5 mol%, 4 mol%, 3 mol%, 2 mol%, 1 mol%, 0.5 mol%, 0.1 mol%, 0.05 mol%, 0.01 mol%, 0 mol%, etc. In one embodiment, the content is preferably 0 mol% to 15 mol%.

[0141] The "sulfonic acid group-containing non-hydrocarbon monomer" refers to a monomer containing atoms other than carbon atoms and hydrogen atoms in its structure other than a sulfonic acid (salt) group.

[0142] Examples of the sulfonic acid group-containing non-hydrocarbon monomer include 2-sulfoethyl (meth)acrylate and tert-butyl (meth)acrylamide sulfonate.

[0143] Examples of the mass % content (sulfonic acid group-containing non-hydrocarbon monomer units / polymer anionic emulsifier) ​​include 15 mass %, 10 mass %, 9 mass %, 8 mass %, 7 mass %, 6 mass %, 5 mass %, 4 mass %, 3 mass %, 2 mass %, 1 mass %, 0.5 mass %, 0.1 mass %, 0.05 mass %, 0.01 mass %, and 0 mass %. In one embodiment, the content is preferably 0 mass % to 15 mass %.

[0144] The mole % content (sulfonic acid group-containing non-hydrocarbon monomer unit / polymer anionic emulsifier) ​​includes 15 mole %, 10 mole %, 9 mole %, 8 mole %, 7 mole %, 6 mole %, 5 mole %, 4 mole %, 3 mole %, 2 mole %, 1 mole %, 0.5 mole %, 0.1 mole %, 0.05 mole %, 0.01 mole %, 0 mole %, etc. In one embodiment, the content is preferably 0 mole % to 15 mole %.

[0145] Phosphoric acid-containing monomers

[0146] The phosphoric acid group-containing monomers may be used alone or in combination of two or more.

[0147] Examples of the phosphoric acid group-containing monomer include mono[2-hydroxyethyl(meth)acrylate] acid phosphate, mono[2-hydroxypropyl(meth)acrylate] acid phosphate, mono[3-hydroxypropyl(meth)acrylate] acid phosphate, mono[2-hydroxypropyl(meth)acrylate] acid phosphate, mono[3-chloro-(meth)acrylate] acid phosphate, (meth)allyl alcohol acid phosphate, and mono[2-hydroxyethyl(meth)acrylate] acid phosphite.

[0148] Examples of the mass % content (phosphoric acid group-containing non-hydrocarbon monomer unit / polymer anionic emulsifier) ​​include 15 mass %, 10 mass %, 9 mass %, 8 mass %, 7 mass %, 6 mass %, 5 mass %, 4 mass %, 3 mass %, 2 mass %, 1 mass %, 0.5 mass %, 0.1 mass %, 0.05 mass %, 0.01 mass %, and 0 mass %. In one embodiment, the content is preferably 0 mass % to 15 mass %.

[0149] The mole % content (phosphoric acid group-containing non-hydrocarbon monomer unit / polymer anionic emulsifier) ​​includes 15 mol%, 10 mol%, 9 mol%, 8 mol%, 7 mol%, 6 mol%, 5 mol%, 4 mol%, 3 mol%, 2 mol%, 1 mol%, 0.5 mol%, 0.1 mol%, 0.05 mol%, 0.01 mol%, 0 mol%, etc. In one embodiment, the content is preferably 0 mol% to 15 mol%.

[0150] (Hydrophobic monomer)

[0151] The hydrophobic monomers may be used alone or in combination of two or more.

[0152] Examples of the hydrophobic monomer include (meth)acrylates and aromatic vinyl compounds that do not contain a hydroxyl group.

[0153] Examples of the mass % content (hydrophobic monomer unit / polymer anionic emulsifier) ​​include 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 %, 9 mass %, 8 mass %, 7 mass %, 6 mass %, and 5 mass %. In one embodiment, the content is preferably 5 to 70 mass %.

[0154] Examples of the mol% content (hydrophobic monomer unit / polymer anionic emulsifier) ​​include 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%, 9 mol%, 8 mol%, 7 mol%, 6 mol%, and 5 mol%. In one embodiment, the content is preferably 5 mol% to 70 mol%.

[0155] Hydroxyl-free (meth)acrylate

[0156] The (meth)acrylates not containing a hydroxyl group may be used alone or in combination of two or more.

[0157] Examples of the hydroxyl-free (meth)acrylate include hydroxyl-free linear (meth)acrylate, hydroxyl-free branched (meth)acrylate, hydroxyl-free alicyclic (meth)acrylate, and hydroxyl-free substituted (meth)acrylate.

[0158] Examples of the mass % content (hydroxyl-free (meth)acrylate unit / polymer anionic emulsifier) ​​include 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 %, 0.5 mass %, 0.1 mass %, 0.05 mass %, 0.01 mass %, and 0 mass %. In one embodiment, the content is preferably 0 to 50 mass %.

[0159] Examples of the mol% content (hydroxyl-free (meth)acrylate unit / polymer anionic emulsifier) ​​include 50 mol%, 45 mol%, 40 mol%, 35 mol%, 30 mol%, 25 mol%, 20 mol%, 15 mol%, 10 mol%, 5 mol%, 4 mol%, 2 mol%, 1 mol%, 0.5 mol%, 0.1 mol%, 0.05 mol%, 0.01 mol%, and 0 mol%. In one embodiment, the content is preferably 0 mol% to 50 mol%.

[0160] Examples of the hydroxyl-free linear (meth)acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, n-pentyl (meth)acrylate, hexyl (meth)acrylate, n-octyl (meth)acrylate, nonyl (meth)acrylate, and decyl (meth)acrylate.

[0161] Examples of the mass % content (linear (meth)acrylate unit containing no hydroxyl group / polymer anionic emulsifier) ​​include 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 %, 0.5 mass %, 0.1 mass %, 0.05 mass %, 0.01 mass %, and 0 mass %. In one embodiment, the content is preferably 0 to 50 mass %.

[0162] Examples of the mol% content (linear (meth)acrylate unit containing no hydroxyl group / polymer anionic emulsifier) ​​include 50 mol%, 45 mol%, 40 mol%, 35 mol%, 30 mol%, 25 mol%, 20 mol%, 15 mol%, 10 mol%, 5 mol%, 4 mol%, 2 mol%, 1 mol%, 0.5 mol%, 0.1 mol%, 0.05 mol%, 0.01 mol%, and 0 mol%. In one embodiment, the content is preferably 0 mol% to 50 mol%.

[0163] Examples of the branched (meth)acrylate not containing a hydroxyl group include isopropyl (meth)acrylate, isobutyl (meth)acrylate, isoamyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate.

[0164] Examples of the mass % content (branched (meth)acrylate units containing no hydroxyl group / polymer anionic emulsifier) ​​include 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 %, 0.5 mass %, 0.1 mass %, 0.05 mass %, 0.01 mass %, and 0 mass %. In one embodiment, the content is preferably 0 to 50 mass %.

[0165] Examples of the mol% content (branched (meth)acrylate unit containing no hydroxyl group / polymer anionic emulsifier) ​​include 50 mol%, 45 mol%, 40 mol%, 35 mol%, 30 mol%, 25 mol%, 20 mol%, 15 mol%, 10 mol%, 5 mol%, 4 mol%, 2 mol%, 1 mol%, 0.5 mol%, 0.1 mol%, 0.05 mol%, 0.01 mol%, and 0 mol%. In one embodiment, the content is preferably 0 mol% to 50 mol%.

[0166] Examples of the alicyclic (meth)acrylate not containing a hydroxyl group include cyclohexyl (meth)acrylate.

[0167] Examples of the mass % content (alicyclic (meth)acrylate unit containing no hydroxyl group / polymer anionic emulsifier) ​​include 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 %, 0.5 mass %, 0.1 mass %, 0.05 mass %, 0.01 mass %, and 0 mass %. In one embodiment, the content is preferably 0 to 50 mass %.

[0168] Examples of the mol% content (alicyclic (meth)acrylate unit containing no hydroxyl group / polymer anionic emulsifier) ​​include 50 mol%, 45 mol%, 40 mol%, 35 mol%, 30 mol%, 25 mol%, 20 mol%, 15 mol%, 10 mol%, 5 mol%, 4 mol%, 2 mol%, 1 mol%, 0.5 mol%, 0.1 mol%, 0.05 mol%, 0.01 mol%, and 0 mol%. In one embodiment, the content is preferably 0 mol% to 50 mol%.

[0169] Aromatic vinyl compounds

[0170] The aromatic vinyl compounds may be used alone or in combination of two or more.

[0171] Examples of the aromatic vinyl compound include styrene, α-methylstyrene, p-methylstyrene, vinyltoluene, chlorostyrene, and divinylbenzene.

[0172] Examples of the mass % content (aromatic vinyl compound unit / polymer anionic emulsifier) ​​include 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 %, 0.5 mass %, 0.1 mass %, 0.05 mass %, 0.01 mass %, and 0 mass %. In one embodiment, the content is preferably 0 to 70 mass %.

[0173] Examples of the mol% content (aromatic vinyl compound unit / polymer anionic emulsifier) ​​include 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%, 4 mol%, 2 mol%, 1 mol%, 0.5 mol%, 0.1 mol%, 0.05 mol%, 0.01 mol%, and 0 mol%. In one embodiment, the content is preferably 0 mol% to 70 mol%.

[0174] (Hydrophilic monomers other than those mentioned above)

[0175] In one embodiment, the polymeric anionic emulsifier may optionally contain hydrophilic monomers other than those mentioned above. The hydrophilic monomers other than those mentioned above may be used alone or in combination of two or more.

[0176] Examples of hydrophilic monomers other than those mentioned above include (meth)acrylamide, hydroxyl group-containing (meth)acrylate, and polyalkylene glycol di(meth)acrylate.

[0177] Examples of the mass % content (hydrophilic monomer units other than those described above / polymer anionic emulsifiers) include 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 %, 0.5 mass %, 0.1 mass %, 0.05 mass %, 0.01 mass %, and 0 mass %. In one embodiment, the content is preferably 0 to 90 mass %.

[0178] Examples of the mol% content (hydrophilic monomer units other than those described above / polymer anionic emulsifiers) include 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%, 4 mol%, 2 mol%, 1 mol%, 0.5 mol%, 0.1 mol%, 0.05 mol%, 0.01 mol%, and 0 mol%. In one embodiment, the content is preferably 0 to 90 mol%.

[0179] (Meth)acrylamide

[0180] (Meth)acrylamide can be used alone or in combination of two or more.

[0181] Examples of the mass % content ((meth)acrylamide unit / polymer anionic emulsifier) ​​include 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 %, 0.5 mass %, 0.1 mass %, 0.05 mass %, 0.01 mass %, and 0 mass %. In one embodiment, the content is preferably 0 to 90 mass %.

[0182] Examples of the mole % content ((meth)acrylamide unit / polymer anionic emulsifier) ​​include 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%, 4 mol%, 2 mol%, 1 mol%, 0.5 mol%, 0.1 mol%, 0.05 mol%, 0.01 mol%, and 0 mol%. In one embodiment, the content is preferably 0 to 90 mol%.

[0183] ·Hydroxy-containing (meth)acrylate

[0184] The hydroxyl group-containing (meth)acrylate may be used alone or in combination of two or more.

[0185] Examples of the hydroxyl group-containing (meth)acrylate include 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate.

[0186] Examples of the mass % content (hydroxyl group-containing (meth)acrylate unit / polymer anionic emulsifier) ​​include 30 mass %, 25 mass %, 20 mass %, 15 mass %, 10 mass %, 5 mass %, 4 mass %, 2 mass %, 1 mass %, 0.5 mass %, 0.1 mass %, 0.05 mass %, 0.01 mass %, and 0 mass %. In one embodiment, the content is preferably 0 to 30 mass %.

[0187] Examples of the mol% content (hydroxyl-containing (meth)acrylate unit / polymer anionic emulsifier) ​​include 30 mol%, 25 mol%, 20 mol%, 15 mol%, 10 mol%, 5 mol%, 4 mol%, 2 mol%, 1 mol%, 0.5 mol%, 0.1 mol%, 0.05 mol%, 0.01 mol%, and 0 mol%. In one embodiment, the content is preferably 0 mol% to 30 mol%.

[0188] Polyalkylene glycol di(meth)acrylate

[0189] The polyalkylene glycol di(meth)acrylates may be used alone or in combination of two or more.

[0190] Examples of the polyalkylene glycol di(meth)acrylate include polyethylene glycol di(meth)acrylate and polypropylene glycol di(meth)acrylate.

[0191] Examples of the mass % content (polyalkylene glycol di(meth)acrylate unit / polymer anionic emulsifier) ​​include 5 mass %, 4 mass %, 2 mass %, 1 mass %, 0.5 mass %, 0.1 mass %, 0.05 mass %, 0.01 mass %, and 0 mass %. In one embodiment, the content is preferably 0 to 5 mass %.

[0192] Examples of the mole % content (polyalkylene glycol di(meth)acrylate unit / polymer anionic emulsifier) ​​include 5 mole %, 4 mole %, 2 mole %, 1 mole %, 0.5 mole %, 0.1 mole %, 0.05 mole %, 0.01 mole %, and 0 mole %. In one embodiment, the content is preferably 0 to 5 mole %.

[0193] (Monomers other than those mentioned above: other monomers)

[0194] In one embodiment, the polymeric anionic emulsifier may optionally contain monomers other than those mentioned above (other monomers). Other monomers may be used alone or in combination of two or more.

[0195] Examples of other monomers include amino group-containing (meth)acrylates.

[0196] Examples of the mass % content (other monomer units / polymer anionic emulsifier) ​​include less than 1 mass %, less than 0.5 mass %, less than 0.1 mass %, and 0 mass %.

[0197] Examples of the mol% content (other monomer units / polymer anionic emulsifier) ​​include less than 1 mol%, less than 0.5 mol%, less than 0.1 mol%, and 0 mol%.

[0198] Examples of the weight average molecular weight (polymer anionic emulsifier) ​​include 150,000, 145,000, 140,000, 135,000, 130,000, 125,000, 124,000, 120,000, 115,000, 110,000, 105,000, 100,000, 95,000, 90,000, 85,000, 80,000, 75,000, 70,000, 65,000, 64,000, 60,000, 55,000, 50,000, 45,000, 40,000, 35,000, 30,000, 29,000, 25,000, 20,000, 15,000, and 10,000. In one embodiment, the weight average molecular weight is preferably 10,000 to 150,000.

[0199] Examples of the number average molecular weight (polymer anionic emulsifier) ​​include 10000, 9500, 9000, 8500, 8000, 7500, 7000, 6500, 6000, 5500, 5000, 4500, 4000, 3500, and 3000. In one embodiment, the number average molecular weight is preferably 3000 to 10000, more preferably 5000 to 7500.

[0200] Examples of the mass % content (polymer anionic emulsifier / active energy ray-curable composition non-volatile component) include 20 mass %, 19 mass %, 17 mass %, 15 mass %, 13 mass %, 11 mass %, 10 mass %, 9 mass %, 7 mass %, 5 mass %, 3 mass %, 2 mass %, 1.5 mass %, 1 mass %, 0.9 mass %, 0.7 mass %, 0.5 mass %, 0.3 mass %, 0.1 mass %, 0.09 mass %, 0.07 mass %, 0.05 mass %, 0.03 mass %, and 0.01 mass %. In one embodiment, the content is preferably 0.01 mass % to 20 mass %, and more preferably 0.5 mass % to 10 mass %.

[0201] Examples of the mass ratio (polymer anionic emulsifier / low molecular anionic emulsifier) ​​include 2000, 1750, 1500, 1250, 1000, 750, 500, 250, 100, 75, 50, 25, 10, 9, 7, 5, 3, 2, 1, 0.9, 0.7, 0.5, 0.3, 0.2, 0.1, 0.09, 0.05, 0.02, 0.01, 0.009, 0.007, 0.005, 0.002, 0.001, 0.0009, 0.0007, and 0.0005. In one embodiment, the mass ratio is preferably 0.0005 to 2000, more preferably 0.1 to 5.

[0202] <Poly(meth)acrylate>

[0203] The poly(meth)acrylates may be used alone or in combination of two or more.

[0204] "Poly(meth)acrylate" refers to a compound having two or more (meth)acryloyl groups.

[0205] Examples of the poly(meth)acrylate include (poly)pentaerythritol poly(meth)acrylate, (poly)trimethylolpropane poly(meth)acrylate, (poly)glycerol poly(meth)acrylate, and urethane poly(meth)acrylate.

[0206] Examples of the (poly)pentaerythritol poly(meth)acrylate include pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol di(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol di(meth)acrylate, tripentaerythritol tri(meth)acrylate, tripentaerythritol tetra(meth)acrylate, tripentaerythritol penta(meth)acrylate, tripentaerythritol hexa(meth)acrylate, tripentaerythritol hepta(meth)acrylate, and tripentaerythritol octa(meth)acrylate.

[0207] Examples of the (poly)trimethylolpropane poly(meth)acrylate include trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, di-trimethylolpropane di(meth)acrylate, di-trimethylolpropane tri(meth)acrylate, and di-trimethylolpropane tetra(meth)acrylate.

[0208] Examples of the (poly)glycerol poly(meth)acrylate include glycerol di(meth)acrylate, glycerol tri(meth)acrylate, diglycerol di(meth)acrylate, diglycerol tri(meth)acrylate, and diglycerol tetra(meth)acrylate.

[0209] (urethane poly(meth)acrylate)

[0210] 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 polyisocyanate.

[0211] <Hydryl-containing poly(meth)acrylate>

[0212] Examples of the hydroxyl group-containing poly(meth)acrylate include (poly)pentaerythritol poly(meth)acrylate, (poly)trimethylolpropane poly(meth)acrylate, and (poly)glycerol poly(meth)acrylate.

[0213] The polyisocyanates may be used alone or in combination of two or more.

[0214] Polyisocyanate

[0215] “Polyisocyanate” refers to a compound having two or more isocyanate groups (—N═C═O).

[0216] 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.

[0217] 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.

[0218] Examples of the branched aliphatic polyisocyanate include diethylpentamethylene diisocyanate, trimethylbutylene diisocyanate, trimethylpentamethylene diisocyanate, and trimethylhexamethylene diisocyanate.

[0219] Examples of the alicyclic polyisocyanate include monocyclic alicyclic polyisocyanate, crosslinked alicyclic polyisocyanate, and condensed alicyclic polyisocyanate.

[0220] 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.

[0221] Examples of the cross-linked cycloaliphatic polyisocyanate include tricyclodecylene diisocyanate, adamantylene diisocyanate, and norbornene diisocyanate.

[0222] Examples of the condensed-ring alicyclic polyisocyanate include biscyclodecylene diisocyanate.

[0223] Examples of the aromatic polyisocyanate include monocyclic aromatic polyisocyanate and condensed-ring aromatic polyisocyanate.

[0224] Examples of the monocyclic aromatic polyisocyanate include dialkyldiphenylmethane diisocyanates such as 4,4'-diphenyldimethylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanates such as 4,4'-diphenyltetramethylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-dibenzyl isocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, toluene diisocyanate, xylylene diisocyanate, and m-tetramethylxylylene diisocyanate.

[0225] Examples of the condensed-ring aromatic polyisocyanate include 1,5-naphthylene diisocyanate and the like.

[0226] In one embodiment, the poly(meth)acrylate is preferably (poly)pentaerythritol poly(meth)acrylate, and the reason for this preference is, for example, that curability is improved.

[0227] Examples of the mass % content (poly(meth)acrylate / active energy ray-curable composition non-volatile component) include 99 mass %, 95 mass %, 90 mass %, 85 mass %, 80 mass %, 75 mass %, 70 mass %, 65 mass %, 60 mass %, 55 mass %, and 50 mass %. In one embodiment, the content is preferably 50 mass % to 99 mass %, and more preferably 70 mass % to 99 mass %.

[0228] Water

[0229] Water may be used alone or in combination of two or more.

[0230] Examples of water include ultrapure water, pure water, distilled water, ion-exchanged water, and tap water.

[0231] Examples of the mass % content (water / active energy ray-curable composition) 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 %, 0.9 mass %, 0.7 mass %, and 0.5 mass %. In one embodiment, the content is preferably 0.5 mass % to 99 mass %, and more preferably 10 mass % to 60 mass %.

[0232] <Photopolymerization initiator>

[0233] In one embodiment, the active energy ray-curable composition may optionally contain a photopolymerization initiator. The photopolymerization initiators may be used alone or in combination of two or more.

[0234] Examples of the photopolymerization initiator include α-hydroxydimethylacetophenone group-containing photopolymerization initiators, α-hydroxycycloalkylphenones, α-aminoalkylphenones, benzyldimethylketal, unsubstituted or substituted alkylphenones, unsubstituted or substituted benzyl groups, unsubstituted or substituted benzophenones, acylphosphine oxides, substituted thioxanthones, and oxime esters.

[0235] Examples of the α-hydroxydimethylacetophenone group-containing photopolymerization initiator include 2-hydroxy-2-methyl-1-phenylpropanone, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-methylpropanone, and 2-hydroxy-1-(4-(4-(2-hydroxy-2-methylpropionyl)benzyl)phenyl)-2-methylpropane-1-one.

[0236] Examples of the α-hydroxycycloalkylphenone include 1-hydroxycyclohexylphenylketone.

[0237] Examples of the α-aminoalkylphenone include 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one.

[0238] Examples of benzyl dimethyl ketal include 2,2-dimethoxy-1,2-diphenylethane-1-one.

[0239] Examples of the unsubstituted or substituted alkylphenone 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-isonitropropiophenone, and 2,2-dimethoxy-1,2-diphenylethane-1-one.

[0240] Examples of the unsubstituted or substituted benzyl group include benzyl and p-anisyl.

[0241] 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.

[0242] Examples of the acylphosphine oxide include 2,4,6-trimethylbenzoyl-diphenylphosphine oxide and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide.

[0243] Examples of the substituted thioxanthone include 2-chlorothioxanthone, 2-isopropylthioxanthone, and 2,4-diethylthioxanthone.

[0244] 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);

[0245] Ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetoxime) (i.e., 1-(((1-(9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl)ethylidene)amino)oxy)ethan-1-one), and the like.

[0246] When electron beam curing is performed, a photopolymerization initiator is not required.

[0247] In one embodiment, the photopolymerization initiator is preferably acylphosphine oxide, and the reason for this preference is, for example, that it produces less precipitation after emulsification.

[0248] Examples of the mass % content (photopolymerization initiator / active energy ray-curable composition non-volatile component) include 30 mass %, 25 mass %, 20 mass %, 15 mass %, 10 mass %, 5 mass %, 4 mass %, 3 mass %, 2 mass %, 1 mass %, 0.9 mass %, 0.7 mass %, 0.5 mass %, 0.3 mass %, 0.1 mass %, and 0 mass %. In one embodiment, the content is preferably 0 mass % to 30 mass %, and more preferably 0.1 mass % to 10 mass %.

[0249] <Additives>

[0250] The active energy ray-curable composition may optionally contain an agent (additive) that does not conform to any of the above.

[0251] Examples of the additives include organic solvents, antioxidants, ultraviolet absorbers, light stabilizers, defoamers, surface conditioners, antifouling agents, pigments, metal oxide fine particle dispersions, and organic fine particle dispersions.

[0252] In one embodiment, the content (additive / active energy ray-curable composition) in parts by mass is preferably 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.

[0253] In one embodiment, the content by mass (additive / any of low molecular weight anionic emulsifier, high molecular weight anionic emulsifier, poly(meth)acrylate, water, photopolymerization initiator) is preferably less than 1 mass part, less than 0.1 mass part, less than 0.01 mass part, 0 mass part, etc.

[0254] Examples of the emulsification method include a machine emulsification method, a phase inversion emulsification method, a forced emulsification method, an inversion emulsification method, and a high-pressure emulsification method.

[0255] Examples of the emulsifying apparatus include a propeller mixer, a turbine mixer, a homomixer, a dispersing mixer, a super mixer, a colloid mill, and a high-pressure homogenizer.

[0256] The order of addition is exemplified by the following order.

[0257] (1) Poly(meth)acrylate and, if necessary, photopolymerization initiator and additives

[0258] (2) Low molecular weight anionic emulsifiers and high molecular weight anionic emulsifiers

[0259] (3) Water

[0260] In one embodiment, the emulsification temperature is preferably 10°C to 80°C.

[0261] In one embodiment, the emulsification time is preferably 1 minute to 24 hours.

[0262] Examples of the kneading concentration include 90 mass%, 89 mass%, 88 mass%, 87 mass%, 86 mass%, 85 mass%, 84 mass%, 83 mass%, 82 mass%, 81 mass%, and 80 mass%. In one embodiment, the kneading concentration is preferably 80 mass% to 90 mass%.

[0263] Examples of the volume average particle size (active energy ray-curable composition) include 10 μm, 7.5 μm, 5 μm, 2.5 μm, 1 μm, 0.9 μm, 0.8 μm, 0.7 μm, 0.6 μm, 0.5 μm, 0.4 μm, 0.3 μm, 0.2 μm, 0.1 μm, 0.05 μm, 0.01 μm, 0.005 μm, and 0.001 μm. In one embodiment, the volume average particle size is preferably 0.1 μm to 10 μm, and more preferably 0.05 μm to 1 μm. This is preferably due to, for example, the reduction of sedimentation.

[0264] The volume average particle size can be measured according to the following conditions.

[0265] Measuring machine: MICROTRAC NT 3300 (manufactured by Nikkiso Co., Ltd.)

[0266] Number of measurements: 3

[0267] Measurement temperature: 25±5℃

[0268] Measurement time: 30 seconds

[0269] Particle size classification: Standard

[0270] Calculation mode: MT3000II

[0271] Measurement upper limit: 2000μm

[0272] Determination limit: 0.021μm

[0273] Residual ratio: 0.00%

[0274] Pass rate: 0.00%

[0275] Residual score ratio setting: Invalid

[0276] Particle permeability:

[0277] Particle shape: non-spherical

[0278] Examples of the viscosity (active energy ray-curable composition) include 500,000 mPa·s, 300,000 mPa·s, 250,000 mPa·s, 100,000 mPa·s, 75,000 mPa·s, 50,000 mPa·s, 25,000 mPa·s, 10,000 mPa·s, 7,500 mPa·s, 5,000 mPa·s, 2,000 mPa·s, and 1,000 mPa·s. In one embodiment, the viscosity is preferably 1,000 mPa·s to 500,000 mPa·s, and more preferably 5,000 mPa·s to 300,000 mPa·s. This is preferred because of, for example, improved curability.

[0279] The viscosity can be measured according to the following conditions.

[0280] Measuring equipment: VISCOMETER TVK-10, manufactured by Toki Industry Co., Ltd.

[0281] Non-volatile matter concentration: 15% by mass

[0282] Measurement temperature: 25°C

[0283] Examples of applications (active energy ray-curable composition) include coating agents and adhesives.

[0284] [Hardened material]

[0285] The present disclosure relates to a cured product of the active energy ray-curable composition.

[0286] Examples of the curing conditions include the following conditions.

[0287] [Laminated material]

[0288] The present disclosure relates to a laminate comprising the hardened object.

[0289] In one embodiment, the laminate can be produced by a method including the following steps.

[0290] Coating step: a step of coating the composition on at least one surface of a substrate. Active energy ray curing step: a step of irradiating active energy rays to form a cured layer.

[0291] Examples of the substrate include polycarbonate films, acrylic films (such as polymethyl methacrylate films), polystyrene films, polyester films, polyolefin films, epoxy resin films, melamine resin films, triacetylcellulose films, acrylonitrile-butadiene-styrene (ABS) films, acrylonitrile-styrene (AS) films, norbornene-based resin films, cyclic olefin films, and polyvinyl alcohol films.

[0292] In one embodiment, the thickness (base material) is preferably 10 μm to 2000 μm.

[0293] In one embodiment, the thickness (hardened material layer) is preferably 0.1 μm to 20 μm.

[0294] (Coating process)

[0295] Examples of the coating method include rod coater coating, wire bar coating, Mayer bar coating, air knife coating, gravure coating, reverse gravure coating, flow coating, offset printing, flexographic printing, and screen printing.

[0296] (Active energy ray curing process)

[0297] Examples of active energy rays include ultraviolet rays and electron beams.

[0298] Examples of ultraviolet light sources include xenon lamps, high-pressure mercury lamps, and metal halide lamps.

[0299] When a high-pressure mercury lamp is used, preferred curing conditions include the following conditions.

[0300] Lamp output: 25W / cm2~160W / cm2

[0301] Ultraviolet (UV) illumination: 10mW / cm 2 ~800mW / cm 2

[0302] Cumulative light intensity: 25mJ / cm 2 ~2000mJ / cm 2

[0303] Conveying speed: 1m / min~50m / min

[0304] When an electron beam is used, preferred curing conditions include the following conditions.

[0305] Accelerating voltage: 10kV~300kV

[0306] Conveying speed: 5m / min~50m / min

[0307] [Example]

[0308] The present invention is described in detail below using examples and comparative examples. However, the 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, all values ​​such as parts and percentages are by mass.

[0309] Preparation Example 1: Polymeric anionic emulsifier

[0310] In a reaction vessel equipped with a thermometer, a stirrer, a cooling tube, a dropping funnel, and a nitrogen inlet tube, 25.0 g of itaconic acid, 0.13 g of sodium methallylsulfonate, 13.2 g of sodium styrenesulfonate, 77.32 g of acrylamide, 5.9 g of 2-ethylhexyl acrylate, 37.7 g of cyclohexyl methacrylate, 220 g of water, 250 g of isopropyl alcohol, and 0.5 g of 2-mercaptoethanol were placed. The mixture was stirred while bubbling nitrogen gas and heated to 50°C. Next, 2.2 g of ammonium persulfate (APS) was added, the temperature was raised to 80°C, and the mixture was stirred for 180 minutes. Furthermore, water vapor was blown in to distill off the isopropyl alcohol. Water was then added to a solids concentration of 25%, and the mixture was cooled to obtain a polymeric anionic emulsifier.

[0311] Unless otherwise specified, other examples may be changed as shown in the following table, and the same procedures as described above may be followed.

[0312] [Table 1]

[0313]

[0314] MAA: Methacrylic acid

[0315] IA: itaconic acid

[0316] SMAS: Sodium Methyl Allyl Sulfonate

[0317] NaSS: Sodium styrene sulfonate

[0318] AM: Acrylamide

[0319] HPA: 3-Hydroxypropyl acrylate

[0320] 6EGA: Product name "New Frontier PE-300," manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd., polyethylene glycol diacrylate

[0321] MMA: Methyl Methacrylate

[0322] 2EHA: 2-ethylhexyl acrylate

[0323] CHMA: Cyclohexyl methacrylate

[0324] St:Styrene

[0325] αSt: α-methylstyrene

[0326] The weight average molecular weight is measured under the following conditions.

[0327] Measuring instrument: GPC (model: HLC-8220) manufactured by Tosoh Co., Ltd.

[0328] Column: Tosoh Corporation's guard column, TSK gel guard column α (1 column) and TSK-GEL α-M (2 columns) (temperature 40°C)

[0329] Detector: TDA Model 301 manufactured by VISCOTECH (concentration detector, 90° light scattering detector, and viscosity detector (temperature 40°C)) RALLS method

[0330] Eluent: 0.02M NaNO3 / CH3CN=80 / 20wt%

[0331] Sample concentration: 0.5wt%

[0332] Development temperature: 40℃

[0333] Standard substance: polyethylene oxide

[0334] Flow rate: 1.0 mL / min

[0335] Measurement Sample: First, prepare the measurement sample by adding the eluent to a non-volatile concentration of 0.5%. Next, add sodium hydroxide aqueous solution until the pH reaches 10-12. Then, immerse in a hot water bath at 80°C or higher for 1 hour. Then, adjust the pH to 6-8 with sulfuric acid and dilute to 0.025% with the eluent before measurement.

[0336] Example 1: Active Energy Ray-Curing Composition

[0337] 100 parts of dipentaerythritol hexaacrylate and 3 parts of 2,4,6-trimethylbenzoyldiphenylphosphine oxide were placed in a flask equipped with a stirrer, a thermometer, and a reflux cooler. The mixture was stirred uniformly at 85°C for 1 hour until completely dissolved. Then, while maintaining the temperature at 40°C, 1 part of a low-molecular-weight anionic emulsifier (RE-1000L), 1 part of a high-molecular-weight anionic emulsifier (Production Example 1), and 4.7 parts of water were added and kneaded at 40°C for 1 hour. Subsequently, 44.6 parts of water were gradually added to adjust the nonvolatile content, and the mixture was emulsified to obtain an active energy ray-curable composition (nonvolatile content concentration 50% by mass).

[0338] Unless otherwise specified, other examples may be changed as shown in the following table, and the same procedures as described above may be followed.

[0339] [Table 2]

[0340]

[0341] 2,4,6-Trimethylbenzoyldiphenylphosphine oxide: Omnirad TPO, manufactured by IGM Resins

[0342] RE-1000L: Product name "Amino Ion RE-1000L", manufactured by Nippon Emulsifier Co., Ltd., ethylene oxide sulfonate ammonium methacrylate containing a polycyclic phenyl skeleton

[0343] S-70: Product name "NEO-HITENOL S-70", manufactured by Daiichi Industrial Pharmaceutical Co., Ltd., sodium polyoxyethylene alkyl sulfosuccinate

[0344] F-13: Product name "NEO-HITENOL F-13", manufactured by Daiichi Industrial Pharmaceutical Co., Ltd., polyoxyethylene alkyl sodium sulfosuccinate containing a styrene skeleton

[0345] N-707: Product name "Newcol 707," manufactured by Nippon Emulsifier Co., Ltd., an anionic emulsifier

[0346] DPHA: Dipentaerythritol hexaacrylate, product name "Miramer M600," manufactured by MIWON

[0347] 40H: Multifunctional urethane acrylate, product name "DPHA-40H", manufactured by Nippon Kayaku Co., Ltd.

[0348] 9550W: A mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, product name "NK Ester A-9550W," manufactured by Shin-Nakamura Chemical Industry Co., Ltd.

[0349] Emulsification

[0350] <Evaluation Criteria>

[0351] ○: Emulsion is dispersed throughout

[0352] ×: Part of the emulsion is oily

[0353] Mechanical stability

[0354] The active energy ray-curable composition was dispersed under the following conditions.

[0355] Disperser: Disperser (TK HOMO DISPER, manufactured by PRIMIX Co., Ltd.)

[0356] Evaluation temperature: 40℃

[0357] Speed: 3000rpm

[0358] Centrifugal force: 300g

[0359] Spin time: 30 minutes

[0360] <Evaluation Criteria>

[0361] ○: No emulsion separation

[0362] ×: Creaming occurs

[0363] High temperature stability

[0364] The active energy ray-curable composition was kept at 50° C. for three months.

[0365] <Evaluation Criteria>

[0366] ○: No precipitation can be seen visually

[0367] ×: Complete precipitation

Claims

1. An active energy ray-curable composition, The active energy ray-curable composition comprises a low molecular weight anionic emulsifier, a high molecular weight anionic emulsifier, a poly(meth)acrylate, and water. The weight average molecular weight of the low molecular anionic emulsifier is less than 10,000. The weight average molecular weight of the polymer anionic emulsifier is 10,000 to 150,000. 2 . The active energy ray-curable composition according to claim 1 , wherein the low-molecular-weight anionic emulsifier is polyoxyalkylenesulfonate ammonium (meth)acrylate. 3 . A cured product comprising the active energy ray-curable composition according to claim 1 . A laminate comprising the hardened product according to claim 3 .

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