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

Abstract

To provide an active energy ray-curable composition, a cured product, and a laminate.SOLUTION: The active energy ray-curable composition contains two or more polymeric anionic emulsifiers, a poly(meth)acrylate, and water. The weight average molecular weights of the polymeric anionic emulsifiers are 10,000-500,000.SELECTED DRAWING: None

Description

Technical Field

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

Background Art

[0002] Active energy ray curable compositions have been developed to impart functionality to the surfaces of various substrates. In recent years, from the perspective of global environmental protection, aqueous active energy ray curable compositions have been demanded.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] The problem to be solved by the present invention is to provide an active energy ray curable composition having good emulsifying properties.

Means for Solving the Problems

[0005] The following items are provided by the present disclosure. (Item 1) An active energy ray curable composition, wherein the active energy ray curable composition contains two or more polymer anionic emulsifiers, poly(meth)acrylate, and water, and the weight average molecular weight of the polymer anionic emulsifier is from 10,000 to 500,000. Active energy ray curable composition. (Item 2) The active energy ray curable composition according to the above item, wherein the two or more polymer anionic emulsifiers are selected from the group consisting of a polymer anionic emulsifier containing (meth)acrylic acid units, a polymer anionic emulsifier containing itaconic acid units, and a polymer anionic emulsifier containing maleic acid units. (Item 3) The cured product of the active energy ray curable composition according to any one of the above items. (Item 4) A laminate containing the cured product according to the above item.

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

[0007] The active energy ray curable composition of the present invention exhibits good emulsifying properties. [Mode for Carrying Out the Invention]

[0008] Throughout the present disclosure, the ranges of numerical values such as physical property values and contents can be set as appropriate (for example, selected from the values described in each of the following items). Specifically, for the numerical value α, when A3, A2, A1 (where A3 > A2 > A1) etc. are listed, the range of the numerical value α is A3 or less, A2 or less, less than A3, less than A2, A1 or more, A2 or more, greater than A1, greater than A2, A1 to A2 (A1 or more and A2 or less), A1 to A3, A2 to A3, A1 or more and less than A3, A1 or more and less than A2, A2 or more and less than A3, greater than A1 and less than A3, greater than A1 and less than A2, greater than A2 and less than A3, greater than A1 and A3 or less, greater than A1 and A2 or less, greater than A2 and A3 or less, etc.

[0009] As long as the problems to be solved by the present invention are solved, each component, condition, numerical value, etc. are not particularly limited.

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

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

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

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

[0014] "(Meth)allyl" means "allyl and / or methallyl".

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

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

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

[0018] "Branched alkyl group" means a group having no cyclic structure in which at least one hydrogen atom of a linear alkyl group is substituted by an alkyl group.

[0019] Examples of the branched alkyl group include an i-propyl group, a 2-ethylhexyl group, a diethylpentyl group, a trimethylbutyl group, a trimethylpentyl group, a trimethylhexyl group, etc.

[0020] Examples of the cycloalkyl group include a monocyclic cycloalkyl group, a bridged cyclic cycloalkyl group, a fused cyclic cycloalkyl group, and the like. A group in which at least one hydrogen atom of the cycloalkyl group is substituted by an alkyl group is also regarded as a cycloalkyl group.

[0021] "Monocyclic" means a cyclic structure formed by covalent bonds of carbon and having no bridging structure inside. "Fused ring" means a cyclic structure in which two or more monocyclic rings share two atoms (that is, each ring shares only one side (fuses) with each other). "Bridged ring" means a cyclic structure in which two or more monocyclic rings share three or more atoms.

[0022] Examples of the monocyclic cycloalkyl group include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclodecyl group, a 3,5,5-trimethylcyclohexyl group, and the like.

[0023] Examples of the bridged cyclic cycloalkyl group include a tricyclodecyl group, an adamantyl group, a norbornyl group, and the like.

[0024] The alkyl group 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 and the like.

[0025] The cycloalkylalkyl group is represented by the following formula. R calkyl -R alkyl - (In the formula, R calkyl represents a cycloalkyl group. R alkyl represents an alkyl group.)

[0026] Examples of the alkylene group include a linear alkylene group, a branched alkylene group, a cycloalkylene group, and the like.

[0027] Examples of the linear 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, an n-decamethylene group, and the like.

[0028] Examples of the branched alkylene group include a diethylpentylene group, a trimethylbutylene group, a trimethylpentylene group, a trimethylhexylene group, and the like.

[0029] Examples of the cycloalkylene group include a monocyclic cycloalkylene group, a bridged-ring cycloalkylene group, a condensed-ring cycloalkylene group, and the like. Further, one or more hydrogen atoms of the cycloalkylene group may be substituted by a linear or branched alkyl group.

[0030] Examples of the monocyclic cycloalkylene group include a cyclopentylene group, a cyclohexylene group, a cycloheptylene group, a cyclodecylene group, a 3,5,5-trimethylcyclohexylene group, and the like.

[0031] Examples of the bridged-ring cycloalkylene group include a tricyclodecylene group, an adamantylene group, a norbornylene group, and the like.

[0032] Examples of the condensed-ring cycloalkylene group include a bicyclodecylene group, and the like.

[0033] The alkylene group also includes a group formed by combining a linear alkylene group, a branched alkylene group, and a cycloalkylene group. Examples of the combined group include a cycloalkylenealkylene group, an alkylenecycloalkylenealkylene group, and the like.

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

[0035] The alkylene cycloalkylene alkylene group is represented by the following formula. -R alkylene -R calkylene -R alkylene - (In the formula, R calkylene represents a cycloalkylene group. R alkylene represents an alkylene group.)

[0036] The aromatic group (aryl group, arylene group) may or may not be substituted. Examples of the substituent of the aromatic group include an alkyl group, a thioalkyl group, a thioaryl group, a carbonylaryl group, etc.

[0037] Examples of the aryl group include a monocyclic aryl group, a condensed-ring aryl group, etc.

[0038] Examples of the monocyclic aryl group include a phenyl group, a tolyl group, a mesityl group, etc.

[0039] Examples of the condensed-ring aryl group include a naphthyl group, etc.

[0040] Examples of the arylene group include a monocyclic arylene group, a condensed-ring arylene group, etc.

[0041] Examples of the monocyclic arylene group include a phenylene group, a tolylene group, etc.

[0042] Examples of the condensed-ring arylene group include a naphthylene group, etc.

[0043] [Active energy ray curable composition] The present disclosure relates to an active energy ray curable composition, wherein the active energy ray curable composition contains two or more kinds of polymer anionic emulsifiers, poly(meth)acrylate and water, and the weight average molecular weight of the polymer anionic emulsifier is 10,000 to 500,000. It relates to an active energy ray curable composition.

[0044] <Polymeric anionic emulsifier> Examples of the polymeric anionic emulsifier include polymers containing anionic group-containing monomer units and hydrophobic monomer units, and the like.

[0045] (Anionic group-containing monomer) The anionic group-containing monomer can be used alone or in combination of two or more.

[0046] Examples of the anionic group-containing monomer include carboxyl group-containing monomers, sulfonic acid group-containing monomers, phosphate group-containing monomers, and salts thereof.

[0047] The mass% content (anionic group-containing monomer unit / polymeric anionic emulsifier) is, for example, 95% by mass, 90% by mass, 85% by mass, 80% by mass, 75% by mass, 70% by mass, 65% by mass, 60% by mass, 55% by mass, 50% by mass, 45% by mass, 40% by mass, 35% by mass, 30% by mass, 25% by mass, 20% by mass, 15% by mass, 10% by mass, 5% by mass, and the like. In one embodiment, the above content is preferably 5% by mass to 95% by mass.

[0048] The mol% content (anionic group-containing monomer unit / polymeric anionic emulsifier) is, 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%, and the like. In one embodiment, the above content is preferably 5 mol% to 95 mol%.

[0049] Examples of the salt include inorganic salts, organic salts, and the like.

[0050] "Inorganic salt" means a salt in which the cationic part is a metal cation.

[0051] Examples of the inorganic salt include sodium salts, lithium salts, calcium salts, and the like.

[0052] Examples of the organic salts include ammonium salts, amine salts and the like.

[0053] · Carboxyl group-containing monomer The carboxyl group-containing monomer can be used alone or in combination of two or more.

[0054] Examples of the carboxyl group-containing monomer include a mono(carboxyl group)-containing monomer, a poly(carboxyl group)-containing monomer and the like.

[0055] The "mono(carboxyl group)-containing monomer" means a monomer having one carboxyl group.

[0056] The "poly(carboxyl group)-containing monomer" means a monomer having a plurality of carboxyl groups.

[0057] The mass% content (carboxyl group-containing monomer unit / polymer anionic emulsifier) is, 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% and the like. In one embodiment, the above content is preferably 0 mass% to 95 mass%.

[0058] The molar% content (carboxyl group-containing monomer unit / polymeric 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 above content preferably includes 0 mol% to 95 mol%.

[0059] The mono (carboxyl group)-containing monomer unit includes, for example, (meth)acrylic acid unit, crotonic acid unit, etc.

[0060] The mass% content (mono (carboxyl group)-containing monomer unit / polymeric 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 above content preferably includes 0 mass% to 95 mass%.

[0061] The molar% content (mono (carboxyl group)-containing monomer unit / polymeric 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 above content preferably includes 0 mol% to 95 mol%.

[0062] The mass percentage content ((meth)acrylic acid unit / polymeric anionic emulsifier) is, for example, 95% by mass, 90% by mass, 85% by mass, 80% by mass, 75% by mass, 70% by mass, 65% by mass, 60% by mass, 55% by mass, 50% by mass, 45% by mass, 40% by mass, 35% by mass, 30% by mass, 25% by mass, 20% by mass, 15% by mass, 10% by mass, 5% by mass, 4% by mass, 2% by mass, 1% by mass, 0.5% by mass, 0.1% by mass, 0.05% by mass, 0.01% by mass, 0% by mass, and the like. In one embodiment, the above content is preferably 0% by mass to 95% by mass.

[0063] The molar percentage content ((meth)acrylic acid unit / polymeric anionic emulsifier) is, 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%, and the like. In one embodiment, the above content is preferably 0 mol% to 95 mol%.

[0064] The monomer unit containing poly(carboxyl group) is, for example, itaconic acid unit, maleic acid unit, fumaric acid unit, citraconic acid unit, and the like.

[0065] The mass percentage content (poly(carboxyl group) containing monomer unit / polymeric anionic emulsifier) is, for example, 60% by mass, 55% by mass, 50% by mass, 45% by mass, 40% by mass, 35% by mass, 30% by mass, 25% by mass, 20% by mass, 15% by mass, 10% by mass, 9% by mass, 8% by mass, 7% by mass, 6% by mass, 5% by mass, 4% by mass, 3% by mass, 2% by mass, 1% by mass, 0.5% by mass, 0.1% by mass, 0.05% by mass, 0.01% by mass, 0% by mass, and the like. In one embodiment, the above content is preferably 0% by mass to 60% by mass.

[0066] The molar% content (poly(carboxyl group)-containing monomer unit / polymeric anionic emulsifier) includes, for example, 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%, 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 above content is preferably 0 mol% to 60 mol%.

[0067] The mass% content (itaconic acid unit / polymeric anionic emulsifier) includes, for example, 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%, 5 mass%, 4 mass%, 3 mass%, 2 mass%, 1 mass%, 0.5 mass%, 0.1 mass%, 0.05 mass%, 0.01 mass%, 0 mass%, etc. In one embodiment, the above content is preferably 0 mass% to 60 mass%.

[0068] The molar% content (itaconic acid unit / polymeric anionic emulsifier) includes, for example, 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%, 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 above content is preferably 0 mol% to 60 mol%.

[0069] The mass% content (maleic acid unit / high molecular anionic emulsifier) is, for example, 60% by mass, 55% by mass, 50% by mass, 45% by mass, 40% by mass, 35% by mass, 30% by mass, 25% by mass, 20% by mass, 15% by mass, 10% by mass, 9% by mass, 8% by mass, 7% by mass, 6% by mass, 5% by mass, 4% by mass, 3% by mass, 2% by mass, 1% by mass, 0.5% by mass, 0.1% by mass, 0.05% by mass, 0.01% by mass, 0% by mass, and the like. In one embodiment, the above content is preferably 0% by mass to 60% by mass.

[0070] The molar% content (maleic acid unit / high molecular anionic emulsifier) is, for example, 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%, 5 mol%, 4 mol%, 3 mol%, 2 mol%, 1 mol%, 0.5 mol%, 0.1 mol%, 0.05 mol%, 0.01 mol%, 0 mol%, and the like. In one embodiment, the above content is preferably 0 mol% to 60 mol%.

[0071] In one embodiment, the poly(carboxyl group)-containing monomer unit may be in a state where one or more carboxyl groups are esterified.

[0072] "Poly(carboxyl group)-containing monomer unit without esterification" means a poly(carboxyl group)-containing monomer unit in which no carboxyl group is esterified at all.

[0073] The mass% content (poly(carboxyl group)-containing monomer unit without esterification / high molecular anionic emulsifier) is, for example, 60% by mass, 55% by mass, 50% by mass, 45% by mass, 40% by mass, 35% by mass, 30% by mass, 25% by mass, 20% by mass, 15% by mass, 10% by mass, 9% by mass, 8% by mass, 7% by mass, 6% by mass, 5% by mass, 4% by mass, 3% by mass, 2% by mass, 1% by mass, 0.5% by mass, 0.1% by mass, 0.05% by mass, 0.01% by mass, 0% by mass, and the like. In one embodiment, the above content is preferably 0% by mass to 60% by mass.

[0074] The molar% content (esterification-free poly(carboxyl group)-containing monomer unit / polymer anionic emulsifier) can be, for example, 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%, 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 above content is preferably 0 mol% to 60 mol%.

[0075] The "partially esterified poly(carboxyl group)-containing monomer unit" means a poly(carboxyl group)-containing monomer unit in which some carboxyl groups are esterified.

[0076] Examples of the partially esterified poly(carboxyl group)-containing monomer unit include a partially aliphatic alcohol-esterified poly(carboxyl group)-containing monomer unit.

[0077] Examples of the partially aliphatic alcohol-esterified poly(carboxyl group)-containing monomer unit include a partially linear aliphatic alcohol-esterified poly(carboxyl group)-containing monomer unit, a partially branched aliphatic alcohol-esterified poly(carboxyl group)-containing monomer unit, and a partially cyclic aliphatic alcohol-esterified poly(carboxyl group)-containing monomer unit.

[0078] Examples of the partially linear aliphatic alcohol-esterified poly(carboxyl group)-containing monomer unit include a methanol half-ester maleic acid unit, an ethanol half-ester maleic acid unit, an n-propanol half-ester maleic acid unit, an n-butanol half-ester maleic acid unit, an n-pentanol half-ester maleic acid unit, an n-hexanol half-ester maleic acid unit, etc.

[0079] The partially branched aliphatic alcohol esterified poly(carboxyl group)-containing monomer units include, for example, i-propanol half ester maleic acid units, 2-ethylhexanol half ester maleic acid units, and the like.

[0080] The partially cyclic aliphatic alcohol esterified poly(carboxyl group)-containing monomer units include, for example, cyclohexanol half ester maleic acid units, and the like.

[0081] The mass% content (partially esterified poly(carboxyl group)-containing monomer unit / high molecular weight anionic emulsifier) includes, for example, 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%, 5 mass%, 4 mass%, 3 mass%, 2 mass%, 1 mass%, 0.5 mass%, 0.1 mass%, 0.05 mass%, 0.01 mass%, 0 mass%, and the like. In one embodiment, the above content is preferably 0 mass% to 60 mass%.

[0082] The mol% content (partially esterified poly(carboxyl group)-containing monomer unit / high molecular weight anionic emulsifier) includes, for example, 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%, 5 mol%, 4 mol%, 3 mol%, 2 mol%, 1 mol%, 0.5 mol%, 0.1 mol%, 0.05 mol%, 0.01 mol%, 0 mol%, and the like. In one embodiment, the above content is preferably 0 mol% to 60 mol%.

[0083] Examples of the mass % content (partially aliphatic esterified poly(carboxyl group)-containing monomer unit / polymeric anionic emulsifier) include 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 %, 5 mass %, 4 mass %, 3 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 is preferably 0 mass % to 60 mass %.

[0084] Examples of the molar percentage content (partially aliphatic esterified poly(carboxyl group)-containing monomer unit / polymeric anionic emulsifier) include 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%, 5 mol%, 4 mol%, 3 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 60 mol%.

[0085] Examples of the mass % content (partially linear aliphatic esterified poly(carboxyl group)-containing monomer unit / polymeric anionic emulsifier) include 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 %, 5 mass %, 4 mass %, 3 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 is preferably 0 mass % to 60 mass %.

[0086] The molar% content (partially linear aliphatic esterified poly(carboxyl group)-containing monomer unit / polymeric anionic emulsifier) is, for example, 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%, 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 above content is preferably 0 mol% to 60 mol%.

[0087] The mass% content (partially branched aliphatic esterified poly(carboxyl group)-containing monomer unit / polymeric anionic emulsifier) is, for example, 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%, 5 mass%, 4 mass%, 3 mass%, 2 mass%, 1 mass%, 0.5 mass%, 0.1 mass%, 0.05 mass%, 0.01 mass%, 0 mass%, etc. In one embodiment, the above content is preferably 0 mass% to 60 mass%.

[0088] The molar% content (partially branched aliphatic esterified poly(carboxyl group)-containing monomer unit / polymeric anionic emulsifier) is, for example, 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%, 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 above content is preferably 0 mol% to 60 mol%.

[0089] Examples of the mass % content (partially cyclic aliphatic esterified poly(carboxyl group)-containing monomer unit / polymeric anionic emulsifier) include 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 %, 5 mass %, 4 mass %, 3 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 is preferably 0 mass % to 60 mass %.

[0090] Examples of the molar percentage content (partially cyclic aliphatic esterified poly(carboxyl group)-containing monomer unit / polymeric anionic emulsifier) include 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%, 5 mol%, 4 mol%, 3 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 60 mol%.

[0091] "Fully esterified poly(carboxyl group)-containing monomer unit" means a poly(carboxyl group)-containing monomer unit in which all of the carboxyl groups have been esterified.

[0092] Examples of the mass % content (fully esterified poly(carboxyl group)-containing monomer unit / polymeric anionic emulsifier) include 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 %, 5 mass %, 4 mass %, 3 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 is preferably 0 mass % to 60 mass %.

[0093] The molar percentage content (fully esterified poly(carboxyl group) - containing monomer unit / polymeric anionic emulsifier) can be, for example, 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%, 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 above - mentioned content is preferably from 0 mol% to 60 mol%.

[0094] Regarding the salt, the esterified poly(carboxyl group) - containing monomer unit can be, for example, a partially esterified poly(carboxyl group) - containing monomer inorganic salt unit, a partially esterified poly(carboxyl group) - containing monomer organic salt unit, etc.

[0095] The degree of neutralization (esterified poly(carboxyl group) - containing monomer unit) can be, for example, 100%, 95%, 90%, 85%, 80%, 75%, 70%, 65%, 60%, 55%, 50%, 45%, 40%, 35%, 30%, 25%, 20%, 15%, 10%, 5%, 0%, etc. In one embodiment, the above - mentioned degree of neutralization is preferably from 0% to 100%.

[0096] (Partially or fully) esterified poly(carboxyl group) - containing monomer units can be introduced into the polymeric anionic emulsifier by the following methods. (1) After esterifying the anhydride of the poly(carboxyl group) - containing monomer, polymerization is carried out. (2) After polymerizing the anhydride of the poly(carboxyl group) - containing monomer, esterification is carried out.

[0097] · Sulfonic acid group - containing monomer Sulfonic acid group - containing monomers can be used alone or in combination of two or more.

[0098] Examples of sulfonic acid group-containing monomers include sulfonic acid group-containing aliphatic hydrocarbon monomers, sulfonic acid group-containing aromatic hydrocarbon monomers, and sulfonic acid group-containing non-hydrocarbon monomers.

[0099] Examples of the mass % content (sulfonic acid group-containing monomer unit / polymeric 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 %, 0 mass %, etc. In one embodiment, the content is preferably 0 mass % to 15 mass %.

[0100] Examples of the molar content (sulfonic acid group-containing monomer unit / polymeric anionic emulsifier) include 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%.

[0101] Examples of sulfonic acid group-containing aliphatic hydrocarbon monomers include (meth)allylsulfonic acid.

[0102] Examples of the mass % content (sulfonic acid group-containing aliphatic hydrocarbon monomer unit / polymeric 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 %, 0 mass %, etc. In one embodiment, the content is preferably 0 mass % to 15 mass %.

[0103] Examples of the molar content (sulfonic acid group-containing aliphatic hydrocarbon monomer unit / polymeric anionic emulsifier) include 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%.

[0104] Examples of sulfonic acid group-containing aromatic hydrocarbon monomers include styrene sulfonic acid, vinyl sulfonic acid, and 2-sulfoethyl (meth)acrylate.

[0105] Examples of the mass % content (sulfonic acid group-containing aromatic hydrocarbon monomer unit / polymeric 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 %, 0 mass %, etc. In one embodiment, the content is preferably 0 mass % to 15 mass %.

[0106] Examples of the molar content (sulfonic acid group-containing aromatic hydrocarbon monomer unit / polymeric anionic emulsifier) include 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%.

[0107] The term "sulfonic acid group-containing non-hydrocarbon monomer" refers to a monomer that contains atoms other than carbon atoms and hydrogen atoms in its structure other than the sulfonic acid (salt) group.

[0108] Examples of sulfonic acid group-containing non-hydrocarbon monomers include 2-sulfoethyl (meth)acrylate and (meth)acrylamido t-butylsulfonic acid.

[0109] The mass percentage content (sulfonic acid group-containing non-hydrocarbon monomer unit / polymer anionic emulsifier) is, for example, 15% by mass, 10% by mass, 9% by mass, 8% by mass, 7% by mass, 6% by mass, 5% by mass, 4% by mass, 3% by mass, 2% by mass, 1% by mass, 0.5% by mass, 0.1% by mass, 0.05% by mass, 0.01% by mass, 0% by mass, etc. In one embodiment, the above content is preferably 0% by mass to 15% by mass.

[0110] The molar percentage content (sulfonic acid group-containing non-hydrocarbon monomer unit / polymer anionic emulsifier) is, for example, 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 above content is preferably 0 mol% to 15 mol%.

[0111] · Phosphoric acid group-containing monomer The phosphoric acid group-containing monomer can be used alone or in combination of two or more.

[0112] The phosphoric acid group-containing monomer is, for example, mono[2-hydroxyethyl (meth)acrylate] acid phosphate, mono[2-hydroxypropyl (meth)acrylate] acid phosphate, mono[3-hydroxypropyl (meth)acrylate] acid phosphate, mono[3-chloro-2-hydroxypropyl (meth)acrylate] acid phosphate, (meth)allyl alcohol acid phosphate, mono[2-hydroxyethyl (meth)acrylate] acid phosphite, etc.

[0113] The mass percentage content (phosphoric acid group-containing non-hydrocarbon monomer unit / polymer anionic emulsifier) is, for example, 15% by mass, 10% by mass, 9% by mass, 8% by mass, 7% by mass, 6% by mass, 5% by mass, 4% by mass, 3% by mass, 2% by mass, 1% by mass, 0.5% by mass, 0.1% by mass, 0.05% by mass, 0.01% by mass, 0% by mass, etc. In one embodiment, the above content is preferably 0% by mass to 15% by mass.

[0114] The molar% content (phosphoric acid group-containing non-hydrocarbon monomer unit / polymeric anionic emulsifier) is, for example, 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 above content is preferably 0 mol% to 15 mol%.

[0115] (Hydrophobic monomer) The hydrophobic monomer can be used alone or in combination of two or more.

[0116] The hydrophobic monomer includes, for example, hydroxyl group-free (meth)acrylate, aromatic vinyl compound, etc.

[0117] The mass% content (hydrophobic monomer unit / polymeric anionic emulsifier) is, for example, 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%, 5 mass%, etc. In one embodiment, the above content is preferably 5 mass% to 70 mass%.

[0118] The molar% content (hydrophobic monomer unit / polymeric anionic emulsifier) is, for example, 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%, 5 mol%, etc. In one embodiment, the above content is preferably 5 mol% to 70 mol%.

[0119] ·Hydroxyl group-free (meth)acrylate The hydroxyl group-free (meth)acrylate can be used alone or in combination of two or more.

[0120] Examples of the hydroxyl group-free (meth)acrylic acid ester include a hydroxyl group-free linear (meth)acrylic acid ester, a hydroxyl group-free branched (meth)acrylic acid ester, a hydroxyl group-free alicyclic (meth)acrylic acid ester, and a hydroxyl group-free substituted (meth)acrylic acid ester.

[0121] Examples of the mass % content (hydroxyl group-free (meth)acrylic acid ester units / polymeric 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 %, 0 mass %, etc. In one embodiment, the content is preferably 0 mass % to 50 mass %.

[0122] Examples of the molar content (hydroxyl group-free (meth)acrylic acid ester units / polymeric 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%.

[0123] Examples of hydroxyl group-free linear (meth)acrylic acid esters include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, n-amyl (meth)acrylate, hexyl (meth)acrylate, n-octyl (meth)acrylate, nonyl (meth)acrylate, and decyl (meth)acrylate.

[0124] Examples of the mass % content (hydroxyl group-free linear (meth)acrylic acid ester units / polymeric 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 %, 0 mass %, etc. In one embodiment, the content is preferably 0 mass % to 50 mass %.

[0125] Examples of the molar content (hydroxyl group-free linear (meth)acrylic acid ester units / polymeric 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%, 0 mol%, etc. In one embodiment, the content is preferably 0 mol% to 50 mol%.

[0126] Examples of the hydroxyl group-free branched (meth)acrylic acid ester include i-propyl (meth)acrylate, i-butyl (meth)acrylate, i-amyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate.

[0127] Examples of the mass % content (hydroxyl group-free branched (meth)acrylic acid ester units / polymeric 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 %, 0 mass %, etc. In one embodiment, the content is preferably 0 mass % to 50 mass %.

[0128] The molar% content (hydroxyl group-free branched (meth)acrylate unit / polymeric anionic emulsifier) is, for example, 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 above content is preferably 0 mol% to 50 mol%.

[0129] Examples of the hydroxyl group-free alicyclic (meth)acrylate include cyclohexyl (meth)acrylate and the like.

[0130] The mass% content (hydroxyl group-free alicyclic (meth)acrylate unit / polymeric anionic emulsifier) is, for example, 50 mass%, 45 mass%, 40 mass%, 35 mass%, 30 mass%, 25 mass%, 2X 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 above content is preferably 0 mass% to 50 mass%.

[0131] The molar% content (hydroxyl group-free alicyclic (meth)acrylate unit / polymeric anionic emulsifier) is, for example, 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 above content is preferably 0 mol% to 50 mol%.

[0132] · Aromatic vinyl compound The aromatic vinyl compound can be used alone or in combination of two or more.

[0133] Examples of the aromatic vinyl compound include styrene, α-methylstyrene, p-methylstyrene, vinyltoluene, chlorostyrene, divinylbenzene, and the like.

[0134] The mass% content (aromatic vinyl compound unit / polymer anionic emulsifier) is, for example, 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 above content is preferably 0 mass% to 70 mass%.

[0135] The molar% content (aromatic vinyl compound unit / polymer anionic emulsifier) is, for example, 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 above content is preferably 0 mol% to 70 mol%.

[0136] (Hydrophilic monomers other than the above) In one embodiment, the polymer anionic emulsifier may optionally contain hydrophilic monomers other than the above. The hydrophilic monomers other than the above may be used alone or in combination of two or more.

[0137] Examples of the hydrophilic monomers other than the above include (meth)acrylamide, hydroxyl group-containing (meth)acrylate, polyalkylene glycol di(meth)acrylate, etc.

[0138] The mass% content (hydrophilic monomer unit other than the above / polymer anionic emulsifier) is, for example, 90% by mass, 85% by mass, 80% by mass, 75% by mass, 70% by mass, 65% by mass, 60% by mass, 55% by mass, 50% by mass, 45% by mass, 40% by mass, 35% by mass, 30% by mass, 25% by mass, 20% by mass, 15% by mass, 10% by mass, 5% by mass, 4% by mass, 2% by mass, 1% by mass, 0.5% by mass, 0.1% by mass, 0.05% by mass, 0.01% by mass, 0% by mass, etc. In one embodiment, the above content is preferably 0% by mass to 90% by mass.

[0139] The molar% content (hydrophilic monomer unit other than the above / polymer anionic emulsifier) is, for example, 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 above content is preferably 0 mol% to 90 mol%.

[0140] · (Meth)acrylamide (Meth)acrylamide can be used alone or in combination of two or more.

[0141] The mass% content ((meth)acrylamide unit / polymer anionic emulsifier) is, for example, 90% by mass, 85% by mass, 80% by mass, 75% by mass, 70% by mass, 65% by mass, 60% by mass, 55% by mass, 50% by mass, 45% by mass, 40% by mass, 35% by mass, 30% by mass, 25% by mass, 20% by mass, 15% by mass, 10% by mass, 5% by mass, 4% by mass, 2% by mass, 1% by mass, 0.5% by mass, 0.1% by mass, 0.05% by mass, 0.01% by mass, 0% by mass, etc. In one embodiment, the above content is preferably 0% by mass to 90% by mass.

[0142] Examples of the molar percentage content ((meth)acrylamide units / polymeric 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 mol% to 90 mol%.

[0143] Hydroxyl group-containing (meth)acrylic acid ester The hydroxyl group-containing (meth)acrylic acid esters may be used alone or in combination of two or more.

[0144] Examples of hydroxyl group-containing (meth)acrylic acid esters include 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate.

[0145] Examples of the mass % content (hydroxyl group-containing (meth)acrylic acid ester units / polymeric 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 %, 0 mass %, etc. In one embodiment, the content is preferably 0 mass % to 30 mass %.

[0146] Examples of the molar content (hydroxyl group-containing (meth)acrylic acid ester units / polymeric 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%, etc. In one embodiment, the content is preferably 0 mol% to 30 mol%.

[0147] Polyalkylene glycol di(meth)acrylate The polyalkylene glycol di(meth)acrylate can be used alone or in combination of two or more thereof.

[0148] Examples of the polyalkylene glycol di(meth)acrylate include polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, and the like.

[0149] Examples of the mass% content (polyalkylene glycol di(meth)acrylate unit / high molecular weight anionic emulsifier) include 5 mass%, 4 mass%, 2 mass%, 1 mass%, 0.5 mass%, 0.1 mass%, 0.05 mass%, 0.01 mass%, 0 mass%, and the like. In one embodiment, the above content is preferably 0 mass% to 5 mass%.

[0150] Examples of the mol% content (polyalkylene glycol di(meth)acrylate unit / high molecular weight anionic emulsifier) include 5 mol%, 4 mol%, 2 mol%, 1 mol%, 0.5 mol%, 0.1 mol%, 0.05 mol%, 0.01 mol%, 0 mol%, and the like. In one embodiment, the above content is preferably 0 mol% to 5 mol%.

[0151] (Monomers other than the above: Other monomers) In one embodiment, the high molecular weight anionic emulsifier may optionally contain monomers other than the above (other monomers). The other monomers can be used alone or in combination of two or more thereof.

[0152] Examples of the other monomers include amino group-containing (meth)acrylate esters and the like.

[0153] Examples of the mass% content (other monomer unit / high molecular weight anionic emulsifier) include less than 1 mass%, less than 0.5 mass%, less than 0.1 mass%, 0 mass%, and the like.

[0154] Examples of the mol% content (other monomer unit / high molecular weight anionic emulsifier) include less than 1 mol%, less than 0.5 mol%, less than 0.1 mol%, 0 mol%, and the like.

[0155] The weight average molecular weight (of the polymeric anionic emulsifier) is, for example, 500,000, 450,000, 400,000, 350,000, 300,000, 250,000, 200,000, 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, 10,000, etc. In one embodiment, the above weight average molecular weight is preferably from 10,000 to 500,000, more preferably from 10,000 to 150,000.

[0156] The number average molecular weight (of the polymeric anionic emulsifier) is, for example, 10,000, 9,500, 9,000, 8,500, 8,000, 7,500, 7,000, 6,500, 6,000, 5,500, 5,000, 4,500, 4,000, 3,500, 3,000, etc. In one embodiment, the above number average molecular weight is preferably from 3,000 to 10,000, more preferably from 5,000 to 7,500.

[0157] The weight average molecular weight and the number average molecular weight can be measured under the following conditions. Measuring instrument: GPC (Model: HLC - 8220) manufactured by Tosoh Corporation Column: One guard column TSKgel guardcolumn α and two columns TSK - GEL α - M manufactured by Tosoh Corporation (temperature 40°C) Detector: TDA MODEL301 manufactured by BiscoTech (concentration detector, 90° light scattering detector and viscosity detector (temperature 40°C)), RALLS method Eluent: 0.02M NaNO3 / CH3CN = 80 / 20 wt% Sample concentration: 0.5 wt% Developing temperature: 40°C Standard substance: Polyethylene oxide Flow rate: 1.0 mL / min Measurement sample: First, prepare the measurement sample by adding the eluent so that the concentration of the measurement sample is 0.5% in terms of the non-volatile content. Next, add an aqueous sodium hydroxide solution until the pH reaches 10 to 12. Further, immerse it in a hot water bath at 80 °C or higher for 1 hour. Then, adjust the pH to 6 to 8 with sulfuric acid and dilute it to 0.025% with the eluent for measurement.

[0158] The mass% content (total of polymer anionic emulsifiers / non-volatile content of the active energy ray curable composition) is, for example, 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%, 0.01 mass%, etc. In one embodiment, the above content is preferably 0.01 mass% to 20 mass%, more preferably 0.5 mass% to 10 mass%.

[0159] <Type (polymer emulsifier)> In one embodiment, two or more polymer anionic emulsifiers are selected from the group consisting of (meth) acrylic acid unit-containing polymer anionic emulsifiers, itaconic acid unit-containing polymer anionic emulsifiers, and maleic acid unit-containing polymer anionic emulsifiers.

[0160] Examples of the combination of two or more polymer anionic emulsifiers include the following.

Table A1

Table A2

Table B1

Table B2

[0161] Examples of the mass % content ((meth)acrylic acid unit-containing polymeric anionic emulsifier / polymeric anionic emulsifier total) include 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 is preferably 0 mass % to 80 mass %.

[0162] Examples of the mass % content (itaconic acid unit-containing polymeric anionic emulsifier / polymeric anionic emulsifier total) include 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 is preferably 0 mass % to 80 mass %.

[0163] Examples of the mass % content (maleic acid unit-containing polymeric anionic emulsifier / polymeric anionic emulsifier total) include 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 is preferably 0 mass % to 80 mass %.

[0164] Examples of the mass ratio (total polymeric anionic emulsifier / poly(meth)acrylate) include 0.5, 0.45, 0.4, 0.35, 0.3, 0.25, 0.2, 0.15, 0.1, 0.06, 0.055, 0.05, 0.04, 0.03, 0.025, 0.02, and 0.01. In one embodiment, the mass ratio is preferably 0.01 to 0.5, and more preferably 0.01 to 0.2.

[0165] <Poly(meth)acrylate> The poly(meth)acrylates may be used alone or in combination of two or more.

[0166] "Poly(meth)acrylate" means a compound having two or more (meth)acryloyl groups.

[0167] Examples of poly(meth)acrylates include (poly)pentaerythritol poly(meth)acrylate, (poly)trimethylolpropane poly(meth)acrylate, (poly)glycerin poly(meth)acrylate, and urethane poly(meth)acrylate.

[0168] Examples of (poly)polypentaerythritol poly(meth)acrylates 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.

[0169] (Poly)trimethylolpropane poly(meth)acrylate includes, for example, trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane di(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, and the like.

[0170] (Poly)glycerin poly(meth)acrylate includes, for example, glycerin di(meth)acrylate, glycerin tri(meth)acrylate, diglycerin di(meth)acrylate, diglycerin tri(meth)acrylate, diglycerin tetra(meth)acrylate, and the like.

[0171] (Urethane poly(meth)acrylate) Urethane poly(meth)acrylate includes, for example, the reaction products of compounds containing hydroxyl group-containing poly(meth)acrylate and polyisocyanate, and the like.

[0172] <Hydroxyl group-containing poly(meth)acrylate> Hydroxyl group-containing poly(meth)acrylate includes, for example, (poly)pentaerythritol poly(meth)acrylate, (poly)trimethylolpropane poly(meth)acrylate, (poly)glycerin poly(meth)acrylate, and the like.

[0173] Polyisocyanate can be used alone or in combination of two or more.

[0174] <Polyisocyanate> "Polyisocyanate" means a compound having two or more isocyanate groups (-N=C=O).

[0175] Polyisocyanate includes, for example, linear aliphatic polyisocyanate, branched aliphatic polyisocyanate, alicyclic polyisocyanate, aromatic polyisocyanate, and their biuret bodies, isocyanurate bodies, allophanate bodies, adduct bodies, and the like.

[0176] Straight-chain aliphatic polyisocyanates include, for example, methylene diisocyanate, dimethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, octamethylene diisocyanate, nonamethylene diisocyanate, decamethylene diisocyanate, etc.

[0177] Branched aliphatic polyisocyanates include, for example, diethylpentylene diisocyanate, trimethylbutylene diisocyanate, trimethylpentylene diisocyanate, trimethylhexamethylene diisocyanate, etc.

[0178] Alicyclic polyisocyanates include, for example, monocyclic alicyclic polyisocyanates, crosslinked alicyclic polyisocyanates, condensed alicyclic polyisocyanates, etc.

[0179] Monocyclic alicyclic polyisocyanates include, for example, hydrogenated xylene diisocyanate, isophorone diisocyanate, cyclopentylene diisocyanate, cyclohexylene diisocyanate, cycloheptylene diisocyanate, cyclodecylene diisocyanate, 3,5,5-trimethylcyclohexylene diisocyanate, dicyclohexylmethane diisocyanate, etc.

[0180] Crosslinked alicyclic polyisocyanates include, for example, tricyclodecylene diisocyanate, adamantane diisocyanate, norbornene diisocyanate, etc.

[0181] Condensed alicyclic polyisocyanates include, for example, bicyclodecylene diisocyanate, etc.

[0182] Aromatic polyisocyanates include, for example, monocyclic aromatic polyisocyanates, condensed-ring aromatic polyisocyanates, etc.

[0183] Monocyclic aromatic polyisocyanates include, for example, dialkyldiphenylmethane diisocyanates such as 4,4'-diphenyldimethylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanates such as 4,4'-diphenyltetramethylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-dibenzyl isocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, m-tetramethylxylylene diisocyanate, and the like.

[0184] Condensed-ring aromatic polyisocyanates include, for example, 1,5-naphthylene diisocyanate and the like.

[0185] In one embodiment, the poly(meth)acrylate is preferably (poly)pentaerythritol poly(meth)acrylate. Preferred reasons include, for example, improved curability and the like.

[0186] The mass% content (poly(meth)acrylate / non-volatile content of the active energy ray curable composition) includes, for example, 99 mass%, 95 mass%, 90 mass%, 85 mass%, 80 mass%, 75 mass%, 70 mass%, 65 mass%, 60 mass%, 55 mass%, 50 mass%, and the like. In one embodiment, the above content is preferably 50 mass% to 99 mass%, more preferably 70 mass% to 99 mass%.

[0187] <Water> Water can be used alone or in combination of two or more.

[0188] Water includes, for example, ultrapure water, pure water, distilled water, ion-exchanged water, tap water, and the like.

[0189] The mass% content (of the active energy ray curable composition) is, for example, 99% by mass, 95% by mass, 90% by mass, 85% by mass, 80% by mass, 75% by mass, 70% by mass, 65% by mass, 60% by mass, 55% by mass, 50% by mass, 45% by mass, 40% by mass, 35% by mass, 30% by mass, 25% by mass, 20% by mass, 15% by mass, 10% by mass, 5% by mass, 4% by mass, 2% by mass, 1% by mass, 0.9% by mass, 0.7% by mass, 0.5% by mass, etc. In one embodiment, the above content is preferably 0.5% by mass to 99% by mass, more preferably 10% by mass to 60% by mass.

[0190] <Photoinitiator> In one embodiment, the active energy ray curable composition may optionally contain a photoinitiator. The photoinitiator can be used alone or in combination of two or more.

[0191] Photoinitiators include, for example, α-hydroxy dimethyl acetophenone group-containing photoinitiators, α-hydroxy cycloalkyl phenyl ketones, α-amino alkyl phenyl ketones, benzyl dimethyl ketal, unsubstituted or substituted alkyl phenyl ketones, unsubstituted or substituted benzyls, unsubstituted or substituted benzophenones, acyl phosphine oxides, substituted thioxanthones, oxime esters, etc.

[0192] α-hydroxy dimethyl acetophenone group-containing photoinitiators include, for example, 2-hydroxy-2-methyl-1-phenylpropanone, 1-[4-(2-hydroxyethoxyl)-phenyl]-2-hydroxy-methylpropanone, 2-hydroxy-1-(4-(4-(2-hydroxy-2-methylpropionyl)benzyl)phenyl)-2-methylpropane-1-one, etc.

[0193] α-hydroxy cycloalkyl phenyl ketones include, for example, 1-hydroxycyclohexyl phenyl ketone, etc.

[0194] α-Aminoalkylphenones include, for example, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one and the like.

[0195] Benzyl dimethyl ketal includes, for example, 2,2-dimethoxy-1,2-diphenylethan-1-one and the like.

[0196] Unsubstituted or substituted alkylphenones include, for example, benzoin methyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin ethyl ether, acetophenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2-phenyl-2-(p-toluenesulfonyloxy)acetophenone, benzoin, 2-benzyl-2-(dimethylamino)-4'-morpholinobutyrophenone, 2-methyl-4'-(methylthio)-2-morpholinopropiophenone, 2-isonitrosoacetophenone, 2,2-dimethoxy-1,2-diphenylethan-1-one and the like.

[0197] Unsubstituted or substituted benzyls include, for example, benzyl, p-anisyl and the like.

[0198] Unsubstituted or substituted benzophenones include, for example, benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-dichlorobenzophenone, 1,4-dibenzoylbenzene, 2-benzoylbenzoic acid, 4-benzoylbenzoic acid, methyl 2-benzoylbenzoate and the like.

[0199] Acylphosphine oxides include, for example, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide and the like.

[0200] Substituted thioxanthones include, for example, 2-chlorothioxanthone, 2-isopropylthioxanthone, 2,4-diethylthioxanthone and the like.

[0201] The oxime ester is, for example, 1,2-octanedione, 1-[4-(phenylthio)-, 2-(O-benzoyloxyimino)] (i.e., 2-((benzoyloxy)imino)-1-(4-(phenylthio)phenyl)octan-1-one); Ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetoxyimino) (i.e., 1-(((1-(9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl)ethylidene)amino)oxy)ethan-1-one), and the like.

[0202] When electron beam curing is carried out, a photoinitiator is not necessary.

[0203] In one embodiment, the photoinitiator preferably includes acylphosphine oxide. The preferable reasons include, for example, few precipitates after emulsification.

[0204] The mass% content (photoinitiator / non-volatile content of the active energy ray curable composition) is, for example, 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%, 0 mass%, and the like. In one embodiment, the above content is preferably 0 mass% to 30 mass%, and more preferably 0.1 mass% to 10 mass%.

[0205] <Additive> The above active energy ray curable composition may optionally contain an agent (additive) that does not correspond to any of the above.

[0206] Additives include, for example, organic solvents, antioxidants, ultraviolet absorbers, light stabilizers, defoamers, surface modifiers, antifouling agents, pigments, metal oxide fine particle dispersions, organic fine particle dispersions, and the like.

[0207] In one embodiment, the parts by mass content (additive / active energy ray curable composition) is preferably less than 1 part by mass, less than 0.1 part by mass, less than 0.01 part by mass, 0 part by mass, etc. [[ID=X]]

[0208] In one embodiment, the parts by mass content (additive / any one of a polymer anionic emulsifier, poly(meth)acrylate, water, and a photopolymerization initiator) is preferably less than 1 part by mass, less than 0.1 part by mass, less than 0.01 part by mass, 0 part by mass, etc.

[0209] Examples of the emulsification method include a mechanical emulsification method, a phase inversion emulsification method, a forced emulsification method, an inverse emulsification method, a high-pressure emulsification method, etc.

[0210] Examples of the emulsification device include a propeller mixer, a turbine mixer, a homomixer, a disperser mixer, an ultra mixer, a colloid mill, a high-pressure homogenizer, etc.

[0211] Examples of the addition order include the following order, etc. (1) Poly(meth)acrylate and, if necessary, a photopolymerization initiator, an additive (2) A polymer anionic emulsifier (3) Water

[0212] In one embodiment, the emulsification temperature is preferably 10°C to 80°C.

[0213] In one embodiment, the emulsification time is preferably 1 minute to 24 hours.

[0214] Examples of the kneading concentration include 90% by mass, 89% by mass, 88% by mass, 87% by mass, 86% by mass, 85% by mass, 84% by mass, 83% by mass, 82% by mass, 81% by mass, 80% by mass, 79% by mass, 78% by mass, 77% by mass, 76% by mass, 75% by mass, etc. In one embodiment, the above kneading concentration is preferably 75% by mass to 90% by mass, more preferably 80% by mass to 90% by mass, and even more preferably 77% by mass to 86% by mass.

[0215] The viscosity (of the active energy ray curable composition) may be, for example, 500000 mPa·s, 300000 mPa·s, 250000 mPa·s, 100000 mPa·s, 75000 mPa·s, 50000 mPa·s, 25000 mPa·s, 10000 mPa·s, 7500 mPa·s, 5000 mPa·s, 2000 mPa·s, 1000 mPa·s, etc. In one embodiment, the above viscosity is preferably 1000 mPa·s to 500000 mPa·s, more preferably 5000 mPa·s to 300000 mPa·s. The preferable reasons include, for example, improvement in curability, etc.

[0216] The viscosity can be measured under the following conditions. Measuring instrument: VISCOMETER TVK-10, manufactured by Toki Sangyo Co., Ltd. Non-volatile content concentration: 15 mass% Measuring temperature: 25 °C

[0217] The use (of the active energy ray curable composition) may be, for example, coating agent, adhesive, active energy ray curable coating agent, active energy ray curable adhesive, etc.

[0218] [Cured product] This disclosure relates to a cured product of the above active energy ray curable composition.

[0219] The curing conditions may be, for example, the following conditions, etc.

[0220] [Laminate] This disclosure relates to a laminate containing the above cured product.

[0221] In one embodiment, the laminate can be manufactured by a method including the following steps. Coating step: A step of coating the above composition on at least one side of a substrate Active energy ray curing step: A step of irradiating active energy rays to form a cured product layer

[0222] Examples of the substrate include polycarbonate film, acrylic film (such as polymethyl methacrylate film), polystyrene film, polyester film, polyolefin film, epoxy resin film, melamine resin film, triacetyl cellulose film, ABS film, AS film, norbornene-based resin film, cyclic olefin film, and polyvinyl alcohol film.

[0223] In one embodiment, the thickness (substrate) is preferably 10 μm to 2000 μm.

[0224] In one embodiment, the thickness (of the cured product layer) is preferably 0.1 μm to 20 μm.

[0225] (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.

[0226] (Active energy ray curing process) Examples of the active energy ray include ultraviolet rays and electron beams.

[0227] Examples of ultraviolet light sources include xenon lamps, high-pressure mercury lamps, and metal halide lamps.

[0228] When a high-pressure mercury lamp is used, the curing conditions are preferably the following conditions. Lamp output: 25W / cm~160W / cm UV illuminance: 10mW / cm 2 ~800mW / cm 2 Accumulated light output: 25mJ / cm 2 ~2000mJ / cm 2 Conveying speed: 1m / min to 50m / min

[0229] When using an electron beam, the curing conditions preferably include the following conditions and the like. Accelerating voltage: 10 kV to 300 kV Conveyor speed: 5 m / min to 50 m / min

Examples

[0230] Hereinafter, the present invention will be specifically described through examples and comparative examples. However, the above description and the following examples are not described for the purpose of limiting the present invention. The present invention is limited only by the scope of the claims. Unless otherwise specified below, numerical values such as parts and % are based on mass.

[0231] Production Example 1: Polymer Anionic Emulsifier Into a reaction vessel equipped with a thermometer, a stirrer, a condenser, a dropping funnel and a nitrogen inlet tube, 25.0 parts of itaconic acid, 0.13 part of sodium methallyl sulfonate, 13.2 parts of sodium styrene sulfonate, 77.32 parts of acrylamide, 5.9 parts of 2-ethylhexyl acrylate, 37.7 parts of cyclohexyl methacrylate, 220 parts of water, 250 parts of isopropyl alcohol and 0.5 part of 2-mercaptoethanol were charged, and the mixture was heated to 50 °C with stirring. Next, 2.2 parts of ammonium persulfate (APS) was added, the temperature was raised to 80 °C, and the mixture was stirred for 3 hours. Water was added and cooled to obtain a polymer anionic emulsifier (non-volatile content 25%).

[0232] Unless otherwise specified, other examples were carried out in the same manner as above except that they were changed as shown in the following table.

[0233] Production Example 3 Into a reaction vessel equipped with a thermometer, a stirring device, a cooling tube, a dropping funnel, and a nitrogen inlet tube, 15 parts of maleic acid, 35 parts of isobutyl alcohol half ester of maleic acid, and 150 parts of toluene were charged while introducing nitrogen. While stirring under a nitrogen stream, the reaction system was heated to 110 °C. Next, 50 parts of styrene were charged into the dropping funnel, and 5.8 parts of t-butyl peroxybenzoate and 35 parts of toluene were charged into another dropping funnel. These were dropped into the vessel from the respective dropping funnels over about 1.5 hours, and the mixture was kept warm under reflux for about 2 hours. Thereafter, 2.3 parts of t-butyl peroxybenzoate and 15 parts of toluene were dropped in over about 30 minutes, and the mixture was further kept warm at the same temperature for 1 hour. Toluene was distilled off under reduced pressure, and the polymer was neutralized with 12.8 parts of sodium hydroxide, a predetermined amount of water, and 81.6 parts of 28% aqueous ammonia to obtain a polymeric anionic emulsifier.

[0234] Production Example 4 Unless otherwise specified, Production Example 4 was carried out in the same manner as Production Example 3, except that it was changed as shown in the following table.

[0235] [Table 1]

[0236] MAA: Methacrylic acid IA: Itaconic acid SMAS: Sodium methallyl sulfonate NaSS: Sodium styrene sulfonate AM: Acrylamide HPA: 3-Hydroxypropyl acrylate Man: Maleic acid Man-nBu: n-Butanol half ester of maleic acid Man-iBu: i-Butanol half ester of maleic acid Man-EH: 2-Ethylhexanol half ester of maleic acid Man-Cy: Cyclohexanol half ester of maleic acid MMA: Methyl methacrylate 2EHA: 2-Ethylhexyl acrylate CHMA: Cyclohexyl methacrylate St: Styrene

[0237] The weight average molecular weight was measured under the following conditions. Measuring instrument: GPC (Model: HLC-8220) manufactured by Tosoh Corporation Column: One guard column TSKgel guardcolumn α and two columns TSK-GEL α-M manufactured by Tosoh Corporation (temperature 40 °C) Detector: TDA MODEL301 manufactured by Bisco Tech Co., Ltd. (concentration detector, 90° light scattering detector and viscosity detector (temperature 40 °C)), RALLS method Eluent: 0.02M NaNO3 / CH3CN = 80 / 20 wt% Sample concentration: 0.5 wt% Developing temperature: 40 °C Standard substance: Polyethylene oxide Flow rate: 1.0 mL / min Measurement sample: First, the eluent was added to the measurement sample so that the concentration of the measurement sample was 0.5% in terms of non-volatile content to prepare the measurement sample. Next, an aqueous sodium hydroxide solution was added until the pH reached 10 - 12. Further, it was immersed in a hot water bath at 80 °C or higher for 1 hour. Then, it was adjusted to pH 6 - 8 with sulfuric acid and diluted to 0.025% with the eluent for measurement.

[0238] Example 1: Active energy ray curable composition Into a flask equipped with a stirrer, a thermometer, and a reflux condenser, 70 parts of DPHA-40H, 30 parts of A-9550W, and 3 parts of a photopolymerization initiator (2,4,6-trimethylbenzoyldiphenylphosphine oxide) were added, and they were uniformly stirred at 85 °C for 1 hour and completely dissolved. Then, while maintaining the temperature at 40 °C, 3 parts of a polymer anionic emulsifier (Production Example 1), 1 part of a polymer anionic emulsifier (Production Example 2), 1 part of RE-1000L, and 4.7 parts of water were added, and they were kneaded at 40 °C for 1 hour. Then, 44.6 parts of water was gradually added for non-volatile content adjustment to perform emulsification, and an active energy ray curable composition (non-volatile content concentration 50 mass%) was obtained.

[0239] Unless otherwise specified, other examples were carried out in the same manner as above, except that they were changed as shown in the following table.

[0240]

Table 2

[0241] 2,4,6-Trimethylbenzoyldiphenylphosphine Oxide: Product name "Omnirad TPO", manufactured by IGM Resins DPHA-40H: Urethane acrylate, product name "KAYARAD DPHA-40H", manufactured by Nippon Kayaku Co., Ltd. Miramer M600: Dipentaerythritol hexaacrylate, product name "Miramer M600", manufactured by Miwon RE-1000L: Product name "Aminoion RE-1000L", manufactured by Nippon Emulsion Co., Ltd., ammonium methacrylate ethylene oxide sulfonate containing polycyclic phenyl skeleton

[0242] The volume average particle size (D90) was measured under the following conditions. Measuring instrument: Microtrac NT 3300 (manufactured by Nikkiso Co., Ltd.) Number of measurements: 3 Measuring temperature: 25 ± 5°C Measuring time: 30 seconds Particle size classification: Standard Calculation mode: MT3000II Measuring upper limit: 2000 μm Measuring lower limit: 0.021 μm Residual ratio: 0.00% Passing ratio: 0.00% Residual ratio setting: Invalid Particle permeability: Permeable Particle shape: Non-spherical

Claims

1. An active energy ray curable composition, wherein the active energy ray curable composition contains two or more kinds of polymer anionic emulsifiers, poly(meth)acrylate, and water, and the weight average molecular weight of the polymer anionic emulsifier is from 10,000 to 500,000, an active energy ray curable composition.

2. The active energy ray curable composition according to Claim 1, wherein the two or more kinds of polymer anionic emulsifiers are selected from the group consisting of a (meth)acrylic acid unit-containing polymer anionic emulsifier, an itaconic acid unit-containing polymer anionic emulsifier, and a maleic acid unit-containing polymer anionic emulsifier.

3. A cured product of the active energy ray curable composition according to Claim 1 or 2.

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

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