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

Abstract

The invention provides an active energy ray-curable composition, a cured product, and a laminate. The active energy ray-curable composition comprises two or more types of polymeric anionic emulsifiers, a poly (meth) acrylate, and water, and the weight average molecular weight of the polymeric anionic emulsifiers is 10,000-500,000.

Description

Technical Field

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

[0002] In order to impart functionality to the surfaces of various substrates, actinic energy ray-curable compositions have been developed. In recent years, from the perspective of environmental protection of the earth, aqueous actinic energy ray-curable compositions have been required.

[0003] [Prior Art Documents]

[0004] [Patent Documents]

[0005] Patent Document 1: Japanese Patent 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 actinic energy ray-curable composition having good emulsifying properties.

[0008] [Technical Means for Solving the Problems]

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

[0010] (Item 1)

[0011] An actinic energy ray-curable composition,

[0012] wherein the actinic energy ray-curable composition contains: two or more kinds of polymeric anionic emulsifiers, poly(meth)acrylate, and water,

[0013] and the weight average molecular weight of the polymeric anionic emulsifier is from 10,000 to 500,000.

[0014] (Item 2)

[0015] The two or more kinds of polymeric anionic emulsifiers are those selected from the group consisting of polymeric anionic emulsifiers containing (meth)acrylic acid units, polymeric anionic emulsifiers containing itaconic acid units, and polymeric anionic emulsifiers containing maleic acid units, in the actinic energy ray-curable composition according to the item.

[0016] (Item 3)

[0017] A cured product of the actinic energy ray-curable composition according to any one of the items.

[0018] (Item 4)

[0019] A laminate comprising the cured product according to the item.

[0020] In the present disclosure, in addition to the explicit combinations, the one or more features may also be provided by further combination.

[0021] [Effects of the Invention]

[0022] The active energy ray curable composition of the present invention exhibits good emulsifying properties. Detailed Description of the Invention

[0023] Throughout the present disclosure, the ranges of physical property values, contents, and other numerical values can be appropriately set (for example, selected from the values described in the following respective items). Specifically, regarding the numerical value α, when A3, A2, A1 (assuming A3 > A2 > A1) etc. are cited as the numerical value α, the range of the numerical value α can be exemplified as being 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.

[0024] As long as the problems to be solved by the present invention are solved, the respective components, conditions, numerical values, etc. are not particularly limited.

[0025] "The amount of αβ (A / B)" means the amount of β (α) of A relative to 100α of B. α is cited, for example, as mass%, mol%, parts by mass, etc. The amount of β is cited, for example, as content, usage amount, etc. "The mass% content (A / B)" means the content (mass%) of A relative to 100 mass% of B.

[0026] "The ratio of γ (A / B)" means the ratio of γ calculated by the formula "A÷B". The ratio of γ is cited, for example, as mass ratio, molar ratio, etc.

[0027] "Non-volatile content" means the total mass of components other than organic solvents and water. In one embodiment, in one embodiment, "the non-volatile components of A" means the total mass of the remaining components when 1 g of A is heated to a constant weight at 105°C.

[0028] "(Meth)acrylic acid" means "acrylic acid and / or methacrylic acid". "(Meth)acrylate" means "acrylate and / or methacrylate". "(Meth)acryloyl" means "acryloyl and / or methacryloyl".

[0029] "(Meth)allyl" means "allyl and / or methallyl".

[0030] “C...” means "having... carbon atoms". For example, "C1-6 alkyl" means an alkyl group having 1 to 6 carbon atoms, and "C6 alkyl" means an alkyl group having 6 carbon atoms.

[0031] Examples of alkyl groups include linear alkyl groups, branched alkyl groups, cycloalkyl groups, etc.

[0032] Examples of linear alkyl groups include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, etc.

[0033] "Branched alkyl" means a group in which at least one hydrogen atom of a linear alkyl group is substituted by an alkyl group and which has no cyclic structure.

[0034] Examples of branched alkyl groups include isopropyl, 2-ethylhexyl, diethylpentyl, trimethylbutyl, trimethylpentyl, trimethylhexyl, etc.

[0035] Examples of cycloalkyl groups include monocyclic cycloalkyl groups, crosslinked cycloalkyl groups, fused cycloalkyl groups, etc. In addition, a group in which at least one hydrogen atom of a cycloalkyl group is substituted by an alkyl group is also regarded as a cycloalkyl group.

[0036] "Monocyclic" means a cyclic structure formed by covalent bonds of carbon atoms and having no bridging structure in the interior. "Fused ring" means a cyclic structure in which two or more monocyclic rings share two atoms (i.e., each ring shares only one edge (fused)). "Crosslinked ring" means a cyclic structure in which two or more monocyclic rings share three or more atoms.

[0037] Examples of monocyclic cycloalkyl groups include cyclopentyl, cyclohexyl, cycloheptyl, cyclodecyl, 3,5,5-trimethylcyclohexyl, etc.

[0038] Examples of crosslinked cycloalkyl groups include tricyclodecyl, adamantyl, norbornyl, etc.

[0039] Furthermore, alkyl groups also include groups combining linear alkyl groups, branched alkyl groups, and cycloalkyl groups. Examples of such combined groups include cycloalkylalkyl, etc.

[0040] Cycloalkylalkyl is represented by the following formula.

[0041] R calkyl -R alkyl -

[0042] (In the formula, R calkyl represents a cycloalkyl group. R alkyl represents an alkyl group.)

[0043] Examples of alkylene groups include linear alkylene groups, branched alkylene groups, cycloalkylene groups, etc.

[0044] Straight-chain alkylene groups include, for example, methylene, ethylene, propylene, n-butylene, n-pentylene, n-hexylene, n-heptylene, n-octylene, n-nonylene, n-decylene, etc.

[0045] Branched alkylene groups include, for example, diethylpentylene, trimethylbutylene, trimethylpentylene, trimethylhexylene, etc.

[0046] Cycloalkylene groups include, for example, monocyclic cycloalkylene groups, crosslinked cycloalkylene groups, fused cycloalkylene groups, etc. In addition, one or more hydrogen atoms of the cycloalkylene group may be substituted with a straight-chain alkyl group or a branched alkyl group.

[0047] Monocyclic cycloalkylene groups include, for example, cyclopentylene, cyclohexylene, cycloheptylene, cyclodecylene, 3,5,5-trimethylcyclohexylene, etc.

[0048] Crosslinked cycloalkylene groups include, for example, tricyclodecylene, adamantylene, norbornylene, etc.

[0049] Fused cycloalkylene groups include, for example, bicyclodecylene, etc.

[0050] Furthermore, alkylene groups also include groups combining straight-chain alkylene groups, branched alkylene groups, and cycloalkylene groups. Examples of such combined groups include cycloalkylalkylene groups, alkylcycloalkylalkylene groups, etc.

[0051] Cycloalkylalkylene groups are represented by the following formula.

[0052] -R calkylene -R alkylene -

[0053] (In the formula, R calkylene represents a cycloalkylene group. R alkylene represents an alkylene group.)

[0054] Alkylcycloalkylalkylene groups are represented by the following formula.

[0055] -R alkylene -R calkylene -R alkylene -

[0056] (In the formula, R calkylene represents a cycloalkylene group. R alkylene represents an alkylene group.)

[0057] Aromatic groups (aryl groups, arylene groups) may be substituted or unsubstituted. Examples of substituents of aryl groups include alkyl groups, thioalkyl groups, thioaryl groups, carbonylaryl groups, etc.

[0058] Aryl groups include, for example, monocyclic aryl groups, fused aryl groups, etc.

[0059] Examples of monocyclic aryl groups include phenyl, tolyl, mesityl, etc.

[0060] Examples of polycyclic aryl groups include naphthyl, etc.

[0061] Examples of arylene groups include monocyclic arylene groups, polycyclic arylene groups, etc.

[0062] Examples of monocyclic arylene groups include phenylene, tolylene group, etc.

[0063] Examples of polycyclic arylene groups include naphthylene, etc.

[0064] [Energy ray curable composition]

[0065] The present disclosure relates to an energy ray curable composition,

[0066] The energy ray curable composition contains: two or more kinds of polymer anionic emulsifiers, poly(meth)acrylate, and water,

[0067] The weight average molecular weight of the polymer anionic emulsifier is 10,000 to 500,000.

[0068] [Polymer anionic emulsifier]

[0069] Examples of polymer anionic emulsifiers include polymers containing anionic group-containing monomer units and hydrophobic monomer units, etc.

[0070] (Anionic group-containing monomer)

[0071] The anionic group-containing monomer can be used alone or two or more kinds can be used.

[0072] Examples of anionic group-containing monomers include carboxyl group-containing monomers, sulfonic acid group-containing monomers, phosphoric acid group-containing monomers, and their salts, etc.

[0073] The mass% content (anionic 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%, etc. In one embodiment, the content preferably selects 5 mass% to 95 mass%.

[0074] The molar percentage content (monomer unit containing an anionic group / 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%, etc. In one embodiment, the content is preferably selected from 5 mol% to 95 mol%.

[0075] Examples of the salt include inorganic salts, organic salts, etc.

[0076] "Inorganic salt" refers to a salt in which the cationic moiety is a metal cation.

[0077] Examples of the inorganic salt include sodium salt, lithium salt, calcium salt, etc.

[0078] Examples of the organic salt include ammonium salt, amine salt, etc.

[0079] · Monomer containing a carboxyl group

[0080] The monomer containing a carboxyl group can be used alone or in combination of two or more.

[0081] Examples of the monomer containing a carboxyl group include a monomer containing a single (carboxyl group), a monomer containing a poly (carboxyl group), etc.

[0082] "Monomer containing a single (carboxyl group)" refers to a monomer having one carboxyl group.

[0083] "Monomer containing a poly (carboxyl group)" refers to a monomer having a plurality of carboxyl groups.

[0084] The mass percentage content (monomer unit containing a carboxyl group / 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 content is preferably selected from 0 mass% to 95 mass%.

[0085] The molar percentage 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 content is preferably selected from 0 mol% to 95 mol%.

[0086] Examples of the monomer unit containing a single (carboxyl group) include a (meth)acrylic acid unit, a crotonic acid unit, etc.

[0087] The mass percentage content (single (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 content is preferably selected from 0 mass% to 95 mass%.

[0088] The molar percentage content (single (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 content is preferably selected from 0 mol% to 95 mol%.

[0089] The mass% content ((meth)acrylic acid 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 content preferably selects 0 mass% to 95 mass%.

[0090] The molar% content ((meth)acrylic acid 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 content preferably selects 0 mol% to 95 mol%.

[0091] The monomer units containing poly(carboxyl group) include, for example, itaconic acid unit, maleic acid unit, fumaric acid unit, citraconic acid unit, etc.

[0092] The mass% content (monomer unit containing poly(carboxyl group) / 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 content preferably selects 0 mass% to 60 mass%.

[0093] The molar percentage content (poly(carboxyl)-containing monomer unit / high molecular 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 content is preferably selected from 0 mol% to 60 mol%.

[0094] The mass percentage content (itaconic acid unit / high molecular 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 content is preferably selected from 0 mass% to 60 mass%.

[0095] The molar percentage content (itaconic acid unit / high molecular 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 content is preferably selected from 0 mol% to 60 mol%.

[0096] The mass percentage content (maleic acid unit / high molecular 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 content is preferably selected from 0 mass% to 60 mass%.

[0097] The molar percentage content (maleic acid unit / high molecular 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 content is preferably selected from 0 mol% to 60 mol%.

[0098] In one embodiment, one or more carboxyl groups of the monomer units contained in the poly(carboxyl group) may be in an esterified state.

[0099] "Poly(carboxyl group)-containing monomer unit without esterification" means a poly(carboxyl group)-containing monomer unit in which the carboxyl group is completely unesterified.

[0100] The mass percentage content (poly(carboxyl group)-containing monomer unit without esterification / high molecular 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 content is preferably selected from 0 mass% to 60 mass%.

[0101] The molar percentage content (poly(carboxyl group)-containing monomer unit without esterification / high molecular 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 content is preferably selected from 0 mol% to 60 mol%.

[0102] "Partially esterified poly(carboxyl group)-containing monomer unit" means a poly(carboxyl group)-containing monomer unit in which a part of the carboxyl groups are esterified.

[0103] Examples of the partially esterified poly(carboxyl group)-containing monomer unit include a partially aliphatic alcohol-esterified poly(carboxyl group)-containing monomer unit, etc.

[0104] Examples of monomer units containing poly(carboxyl) esterified with partial aliphatic alcohols include monomer units containing poly(carboxyl) esterified with partial linear aliphatic alcohols, monomer units containing poly(carboxyl) esterified with partial branched aliphatic alcohols, monomer units containing poly(carboxyl) esterified with partial alicyclic alcohols, and the like.

[0105] Examples of monomer units containing poly(carboxyl) esterified with partial linear aliphatic alcohols include methanol hemiester maleic acid unit, ethanol hemiester maleic acid unit, n-propanol hemiester maleic acid unit, n-butanol hemiester maleic acid unit, n-pentanol hemiester maleic acid unit, n-hexanol hemiester maleic acid unit, and the like.

[0106] Examples of monomer units containing poly(carboxyl) esterified with partial branched aliphatic alcohols include isopropanol maleic hemiester unit, 2-ethylhexanol hemiester maleic acid unit, and the like.

[0107] Examples of monomer units containing poly(carboxyl) esterified with partial alicyclic alcohols include cyclohexanol hemiester maleic acid unit, and the like.

[0108] Examples of the mass% content (partially esterified monomer unit containing poly(carboxyl) / 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%, and the like. In one embodiment, the content preferably selects 0 mass% to 60 mass%.

[0109] Examples of the mole% content (partially esterified monomer unit containing poly(carboxyl) / polymeric anionic emulsifier) include 60 mole%, 55 mole%, 50 mole%, 45 mole%, 40 mole%, 35 mole%, 30 mole%, 25 mole%, 20 mole%, 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%, and the like. In one embodiment, the content preferably selects 0 mole% to 60 mole%.

[0110] The mass% content (partially aliphatically esterified monomer units containing poly(carboxyl) / 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 content is preferably selected from 0 mass% to 60 mass%.

[0111] The mole% content (partially aliphatically esterified monomer units containing poly(carboxyl) / polymeric anionic emulsifier) includes, for example, 60 mole%, 55 mole%, 50 mole%, 45 mole%, 40 mole%, 35 mole%, 30 mole%, 25 mole%, 20 mole%, 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 selected from 0 mole% to 60 mole%.

[0112] The mass% content (partially linear aliphatically esterified monomer units containing poly(carboxyl) / 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 content is preferably selected from 0 mass% to 60 mass%.

[0113] The mole% content (partially linear aliphatically esterified monomer units containing poly(carboxyl) / polymeric anionic emulsifier) includes, for example, 60 mole%, 55 mole%, 50 mole%, 45 mole%, 40 mole%, 35 mole%, 30 mole%, 25 mole%, 20 mole%, 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 selected from 0 mole% to 60 mole%.

[0114] The mass% content (partially branched aliphatic esterified poly(carboxyl)-containing monomer 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 content is preferably selected from 0 mass% to 60 mass%.

[0115] The molar% content (partially branched aliphatic esterified poly(carboxyl)-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 content is preferably selected from 0 mol% to 60 mol%.

[0116] The mass% content (partially alicyclic esterified poly(carboxyl)-containing monomer 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 content is preferably selected from 0 mass% to 60 mass%.

[0117] The molar% content (partially alicyclic esterified poly(carboxyl)-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 content is preferably selected from 0 mol% to 60 mol%.

[0118] "Fully esterified poly(carboxyl)-containing monomer units" refers to poly(carboxyl)-containing monomer units in which all carboxyl groups are esterified.

[0119] The mass% content (fully esterified poly(carboxyl)-containing monomer units / 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 content is preferably selected from 0 mass% to 60 mass%.

[0120] The molar% content (fully esterified poly(carboxyl)-containing monomer units / 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 content is preferably selected from 0 mol% to 60 mol%.

[0121] For salts, esterified poly(carboxyl)-containing monomer units include, for example, partially esterified poly(carboxyl)-containing monomer inorganic salt units, partially esterified poly(carboxyl)-containing monomer organic salt units, etc.

[0122] The degree of neutralization (esterified poly(carboxyl)-containing monomer units) is, 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 degree of neutralization is preferably selected from 0% to 100%.

[0123] (Partially or fully) esterified poly(carboxyl)-containing monomer units can be introduced into the polymeric anionic emulsifier by the following methods.

[0124] (1) After esterifying the anhydride containing the poly(carboxyl) monomer, polymerization is carried out.

[0125] (2) After polymerizing the anhydride containing the poly(carboxyl) monomer, esterification is carried out.

[0126] · Monomers containing sulfonic acid groups

[0127] The monomers containing a sulfonic acid group can be used alone or in combination of two or more.

[0128] Examples of the monomers containing a sulfonic acid group include aliphatic hydrocarbon monomers containing a sulfonic acid group, aromatic hydrocarbon monomers containing a sulfonic acid group, non-hydrocarbon monomers containing a sulfonic acid group, and the like.

[0129] Examples of the mass% content (sulfonic acid group-containing 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%, 0 mass%, and the like. In one embodiment, the content is preferably selected from 0 mass% to 15 mass%.

[0130] Examples of the mole% content (sulfonic acid group-containing monomer unit / polymer anionic emulsifier) include 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%, and the like. In one embodiment, the content is preferably selected from 0 mole% to 15 mole%.

[0131] Examples of the aliphatic hydrocarbon monomers containing a sulfonic acid group include (meth)allyl sulfonic acid and the like.

[0132] 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%, 0 mass%, and the like. In one embodiment, the content is preferably selected from 0 mass% to 15 mass%.

[0133] Examples of the mole% content (sulfonic acid group-containing aliphatic hydrocarbon monomer unit / polymer anionic emulsifier) include 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%, and the like. In one embodiment, the content is preferably selected from 0 mole% to 15 mole%.

[0134] Examples of the aromatic hydrocarbon monomers containing a sulfonic acid group include styrene sulfonic acid, vinyl sulfonic acid, 2-sulfoethyl (meth)acrylate, and the like.

[0135] The mass% content (sulfonic acid group-containing aromatic hydrocarbon monomer unit / polymer anionic emulsifier) includes, for example, 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 selected from 0 mass% to 15 mass%.

[0136] The molar% content (sulfonic acid group-containing aromatic hydrocarbon monomer unit / polymer anionic emulsifier) includes, 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 content is preferably selected from 0 mol% to 15 mol%.

[0137] The "sulfonic acid group-containing non-hydrocarbon monomer" refers to a monomer having atoms other than carbon atoms and hydrogen atoms in the structure other than the sulfonic acid (salt) group.

[0138] Examples of the sulfonic acid group-containing non-hydrocarbon monomer include 2-sulfoethyl (meth)acrylate, tert-butylsulfonic acid (meth)acrylamide, etc.

[0139] The mass% content (sulfonic acid group-containing non-hydrocarbon monomer unit / polymer anionic emulsifier) includes, for example, 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 selected from 0 mass% to 15 mass%.

[0140] The molar% content (sulfonic acid group-containing non-hydrocarbon monomer unit / polymer anionic emulsifier) includes, 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 content is preferably selected from 0 mol% to 15 mol%.

[0141] · Phosphoric acid group-containing monomers

[0142] The phosphoric acid group-containing monomers can be used alone or in combination of two or more.

[0143] Examples of the monomer containing a phosphoric acid group include 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.

[0144] The mass% content (non-hydrocarbon monomer unit containing a phosphoric acid group / high molecular anionic emulsifier) includes, for example, 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 selected from 0 mass% to 15 mass%.

[0145] The mole% content (non-hydrocarbon monomer unit containing a phosphoric acid group / high molecular anionic emulsifier) includes, 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 content is preferably selected from 0 mol% to 15 mol%.

[0146] (Hydrophobic monomer)

[0147] The hydrophobic monomer can be used alone or in combination of two or more.

[0148] Examples of the hydrophobic monomer include (meth)acrylate without a hydroxyl group, aromatic vinyl compounds, etc.

[0149] The mass% content (hydrophobic monomer unit / high molecular anionic emulsifier) includes, 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 content is preferably selected from 5 mass% to 70 mass%.

[0150] The molar percentage content (hydrophobic monomer unit / polymeric anionic emulsifier) includes, 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 content is preferably selected from 5 mol% to 70 mol%.

[0151] · Hydroxy group-free (meth)acrylate

[0152] The hydroxy group-free (meth)acrylate can be used alone or in combination of two or more kinds.

[0153] Examples of the hydroxy group-free (meth)acrylate include hydroxy group-free linear (meth)acrylate, hydroxy group-free branched (meth)acrylate, hydroxy group-free alicyclic (meth)acrylate, hydroxy group-free substituted (meth)acrylate, etc.

[0154] The mass percentage content (hydroxy group-free (meth)acrylate unit / polymeric anionic emulsifier) includes, for example, 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 selected from 0 mass% to 50 mass%.

[0155] The molar percentage content (hydroxy group-free (meth)acrylate unit / polymeric anionic emulsifier) includes, 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 content is preferably selected from 0 mol% to 50 mol%.

[0156] Examples of the hydroxy group-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, decyl (meth)acrylate, etc.

[0157] The mass% content (linear (meth)acrylate unit without hydroxyl group / high molecular anionic emulsifier) includes, for example, 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 selects 0 mass% to 50 mass%.

[0158] The molar% content (linear (meth)acrylate unit without hydroxyl group / high molecular anionic emulsifier) includes, 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 content preferably selects 0 mol% to 50 mol%.

[0159] Branched (meth)acrylate without hydroxyl group includes, for example, isopropyl (meth)acrylate, isobutyl (meth)acrylate, isopentyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, etc.

[0160] The mass% content (branched (meth)acrylate unit without hydroxyl group / high molecular anionic emulsifier) includes, for example, 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 selects 0 mass% to 50 mass%.

[0161] The molar% content (branched (meth)acrylate unit without hydroxyl group / high molecular anionic emulsifier) includes, 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 content preferably selects 0 mol% to 50 mol%.

[0162] Alicyclic (meth)acrylate without hydroxyl group includes, for example, cyclohexyl (meth)acrylate, etc.

[0163] The mass % content (alicyclic (meth)acrylate unit without hydroxyl group / polymer anionic emulsifier) includes, for example, 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 selected from 0 mass% to 50 mass%.

[0164] The molar % content (alicyclic (meth)acrylate unit without hydroxyl group / polymer anionic emulsifier) includes, 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 content is preferably selected from 0 mol% to 50 mol%.

[0165] · Aromatic vinyl compound

[0166] The aromatic vinyl compound can be used alone or in combination of two or more.

[0167] Examples of the aromatic vinyl compound include styrene, α-methylstyrene, p-methylstyrene, vinyltoluene, chlorostyrene, divinylbenzene, etc.

[0168] The mass % content (aromatic vinyl compound unit / polymer anionic emulsifier) includes, 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 content is preferably selected from 0 mass% to 70 mass%.

[0169] The molar % content (aromatic vinyl compound unit / polymer anionic emulsifier) includes, 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 content is preferably selected from 0 mol% to 70 mol%.

[0170] (Hydrophilic monomers other than those described above)

[0171] In one embodiment, the polymeric anionic emulsifier may optionally contain hydrophilic monomers other than those described above. The hydrophilic monomers other than those described above may be used alone or in combination of two or more kinds.

[0172] Examples of the hydrophilic monomers other than those described above include (meth)acrylamide, hydroxy group-containing (meth)acrylate, polyalkylene glycol di(meth)acrylate, and the like.

[0173] The mass% content (hydrophilic monomer unit other than those described above / polymeric anionic emulsifier) includes, for example, 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 content preferably selected is 0 mass% to 90 mass%.

[0174] The molar% content (hydrophilic monomer unit other than those described above / polymeric anionic emulsifier) includes, 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%, and the like. In one embodiment, the content preferably selected is 0 mol% to 90 mol%.

[0175] ·(Meth)acrylamide

[0176] (Meth)acrylamide may be used alone or in combination of two or more kinds.

[0177] The mass% content ((meth)acrylamide unit / polymeric anionic emulsifier) includes, for example, 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 content preferably selected is 0 mass% to 90 mass%.

[0178] The molar percentage content ((meth)acrylamide unit / polymeric anionic emulsifier) includes, 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 content is preferably selected from 0 mol% to 90 mol%.

[0179] · Hydroxy group-containing (meth)acrylate

[0180] The hydroxy group-containing (meth)acrylate can be used alone or in combination of two or more.

[0181] Examples of the hydroxy group-containing (meth)acrylate include 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, etc.

[0182] The mass percentage content (hydroxy group-containing (meth)acrylate unit / polymeric anionic emulsifier) includes, for example, 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 selected from 0 mass% to 30 mass%.

[0183] The molar percentage content (hydroxy group-containing (meth)acrylate unit / polymeric anionic emulsifier) includes, for example, 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 selected from 0 mol% to 30 mol%.

[0184] · Polyalkylene glycol di(meth)acrylate

[0185] The polyalkylene glycol di(meth)acrylate can be used alone or in combination of two or more.

[0186] Examples of the polyalkylene glycol di(meth)acrylate include polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, etc.

[0187] The mass% content (polyalkylene glycol di(meth)acrylate unit / high molecular weight anionic emulsifier) is, for example, 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 selected from 0 mass% to 5 mass%.

[0188] The molar% content (polyalkylene glycol di(meth)acrylate unit / high molecular weight anionic emulsifier) is, for example, 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 selected from 0 mol% to 5 mol%.

[0189] (Monomers other than the above: other monomers)

[0190] In one embodiment, the high molecular weight anionic emulsifier may optionally contain monomers other than the above (other monomers). The other monomers may be used alone or in combination of two or more.

[0191] Examples of the other monomers include amino-containing (meth)acrylate, etc.

[0192] The mass% content (other monomer unit / high molecular weight anionic emulsifier) is, for example, less than 1 mass%, less than 0.5 mass%, less than 0.1 mass%, 0 mass%, etc.

[0193] The molar% content (other monomer unit / high molecular weight anionic emulsifier) is, for example, less than 1 mol%, less than 0.5 mol%, less than 0.1 mol%, 0 mol%, etc.

[0194] The weight average molecular weight (high molecular weight 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 weight average molecular weight is preferably selected from 10,000 to 500,000, and more preferably from 10,000 to 150,000.

[0195] The number average molecular weight (for the high molecular weight 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 number average molecular weight is preferably selected from 3,000 to 10,000, and more preferably from 5,000 to 7,500.

[0196] The weight average molecular weight and the number average molecular weight can be determined according to the following conditions.

[0197] Measuring instrument: manufactured by Tosoh Corporation, GPC (model: HLC-8220)

[0198] Chromatographic column: 1 TSKgel guardcolumn α manufactured by Tosoh Corporation and 2 TSK-GEL α (temperature 40°C)

[0199] Detector: TDA MODEL301 manufactured by Viscotek Corporation (concentration detector, 90° light scattering detector and viscosity detector (temperature 40°C)), RALLS method

[0200] Eluent: 0.02M NaNO3 / CH3CN = 80 / 20 wt%

[0201] Sample concentration: 0.5 wt%

[0202] Developing temperature: 40°C

[0203] Standard substance: polyethylene oxide

[0204] Flow rate: 1.0 mL / min

[0205] Measured sample: First, the measured sample is prepared by adding the eluent to make the concentration of the measured sample 0.5% at the non-volatile content concentration. Then, an aqueous sodium hydroxide solution is added until the pH becomes 10 to 12. In addition, it is immersed in a hot water bath at 80°C or higher for 1 hour. After that, the pH is adjusted to 6 to 8 with sulfuric acid and diluted to 0.025% with the eluent for measurement.

[0206] The mass% content ((total amount of high molecular anionic emulsifier / non-volatile content of the active energy ray curable composition)) includes, 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 content is preferably selected from 0.01 mass% to 20 mass%, and more preferably from 0.5 mass% to 10 mass%.

[0207] <Type (high molecular emulsifier)>

[0208] In one embodiment, two or more high molecular anionic emulsifiers are selected from the group consisting of high molecular anionic emulsifiers containing (meth)acrylic acid units, high molecular anionic emulsifiers containing itaconic acid units, and high molecular anionic emulsifiers containing maleic acid units.

[0209] Examples of the combination of two or more high molecular anionic emulsifiers include the following, etc.

[0210] [Table A]

[0211]

[0212]

[0213] [Table B]

[0214]

[0215]

[0216]

[0217] The mass% content ((high molecular anionic emulsifier containing (meth)acrylic acid units / total amount of high molecular anionic emulsifier)) includes, for example, 80 mass%, 75 mass%, 70 mass%, 65 mass%, 60 mass%, 55 mass%, 50 mass%, 45 mass%, 40 mass%, 35 mass%, 30 mass%, 25 mass%, 20 mass%, 15 mass%, 10 mass%, 5 mass%, 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 selected from 0 mass% to 80 mass%.

[0218] The mass% content (the polymer anionic emulsifier containing itaconic acid units / the total amount of polymer anionic emulsifiers) includes, for example, 80 mass%, 75 mass%, 70 mass%, 65 mass%, 60 mass%, 55 mass%, 50 mass%, 45 mass%, 40 mass%, 35 mass%, 30 mass%, 25 mass%, 20 mass%, 15 mass%, 10 mass%, 5 mass%, 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 selected from 0 mass% to 80 mass%.

[0219] The mass% content (the polymer anionic emulsifier containing maleic acid units / the total amount of polymer anionic emulsifiers) includes, for example, 80 mass%, 75 mass%, 70 mass%, 65 mass%, 60 mass%, 55 mass%, 50 mass%, 45 mass%, 40 mass%, 35 mass%, 30 mass%, 25 mass%, 20 mass%, 15 mass%, 10 mass%, 5 mass%, 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 selected from 0 mass% to 80 mass%.

[0220] The mass ratio (the total amount of polymer anionic emulsifiers / poly(meth)acrylate) includes, for example, 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, 0.01, etc. In one embodiment, the mass ratio is preferably selected from 0.01 to 0.5, and more preferably from 0.01 to 0.2.

[0221] <poly(meth)acrylate>

[0222] The poly(meth)acrylate can be used alone or in combination of two or more.

[0223] "Poly(meth)acrylate" refers to a compound having two or more (meth)acryloyl groups.

[0224] Examples of poly(meth)acrylate include (poly)pentaerythritol poly(meth)acrylate, (poly)trimethylolpropane poly(meth)acrylate, (poly)glycerol poly(meth)acrylate, urethane poly(meth)acrylate, etc.

[0225] (Poly)pentaerythritol poly(meth)acrylate includes, for example, 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, tripentaerythritol octa(meth)acrylate, etc.

[0226] (Poly)trimethylolpropane poly(meth)acrylate includes, for example, trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, di-trimethylolpropane di(meth)acrylate, di-trimethylolpropane tri(meth)acrylate, di-trimethylolpropane tetra(meth)acrylate, etc.

[0227] (Poly)glycerol poly(meth)acrylate includes, for example, glycerol di(meth)acrylate, glycerol tri(meth)acrylate, diglycerol di(meth)acrylate, diglycerol tri(meth)acrylate, diglycerol tetra(meth)acrylate, etc.

[0228] (Urethane poly(meth)acrylate)

[0229] Urethane poly(meth)acrylate includes, for example, reaction products of a compound group including a hydroxyl group-containing poly(meth)acrylate and a polyisocyanate, etc.

[0230] <Hydroxyl group-containing poly(meth)acrylate>

[0231] Hydroxyl group-containing poly(meth)acrylate includes, for example, (poly)pentaerythritol poly(meth)acrylate, (poly)trimethylolpropane poly(meth)acrylate, (poly)glycerol poly(meth)acrylate, etc.

[0232] The polyisocyanate can be used alone or in combination of two or more.

[0233] <Polyisocyanate>

[0234] "Polyisocyanate" refers to a compound having two or more isocyanate groups (-N=C=O).

[0235] Polyisocyanate includes, for example, linear aliphatic polyisocyanate, branched aliphatic polyisocyanate, alicyclic polyisocyanate, aromatic polyisocyanate, and their biuret bodies, isocyanurate bodies, urethane bodies, adduct bodies, etc.

[0236] Examples of linear aliphatic polyisocyanates include methylene diisocyanate, dimethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, octamethylene diisocyanate, nonamethylene diisocyanate, decamethylene diisocyanate, etc.

[0237] Examples of branched aliphatic polyisocyanates include diethylvalylene diisocyanate, trimethylbutylene diisocyanate, trimethylpentylene diisocyanate, trimethylhexamethylene diisocyanate, etc.

[0238] Examples of alicyclic polyisocyanates include monocyclic alicyclic polyisocyanates, crosslinked cyclic alicyclic polyisocyanates, condensed cyclic alicyclic polyisocyanates, etc.

[0239] Examples of monocyclic alicyclic polyisocyanates include hydrogenated xylene diisocyanate, isophorone diisocyanate, cyclopentylene diisocyanate, cyclohexylene diisocyanate, cycloheptylene diisocyanate, cyclodecylene diisocyanate, 3,5,5-trimethylcyclohexylene diisocyanate, dicyclohexylmethane diisocyanate, etc.

[0240] Examples of crosslinked cyclic alicyclic polyisocyanates include tricyclodecene diisocyanate, adamantane diisocyanate, norbornene diisocyanate, etc.

[0241] Examples of condensed cyclic alicyclic polyisocyanates include bicyclodecene diisocyanate, etc.

[0242] Examples of aromatic polyisocyanates include monocyclic aromatic polyisocyanates, condensed cyclic aromatic polyisocyanates, etc.

[0243] Examples of monocyclic aromatic polyisocyanates 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, mesotetramethylxylylene diisocyanate, etc.

[0244] Examples of condensed cyclic aromatic polyisocyanates include 1,5-naphthalene diisocyanate, etc.

[0245] In one embodiment, the poly(meth)acrylate is preferably (poly)pentaerythritol poly(meth)acrylate. The reasons for the preference include, for example, improved curability.

[0246] 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%, etc. In one embodiment, the content is preferably 50 mass% to 99 mass%, and more preferably 70 mass% to 99 mass%.

[0247] <Water>

[0248] Water can be used alone or in combination of two or more.

[0249] Examples of water include ultrapure water, pure water, distilled water, ion-exchanged water, tap water, etc.

[0250] The mass% content (water / 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%, 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%, 0.5 mass%, etc. In one embodiment, the content is preferably 0.5 mass% to 99 mass%, and more preferably 10 mass% to 60 mass%.

[0251] <Photoinitiator>

[0252] 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.

[0253] Examples of the photoinitiator include photoinitiators containing an α-hydroxy dimethylacetophenone group, α-hydroxy cycloalkyl ketones, α-amino alkyl ketones, benzyl dimethyl ketals, unsubstituted or substituted phenyl alkyl ketones, unsubstituted or substituted benzyl benzyls, unsubstituted or substituted benzophenones, acyl phosphine oxides, substituted thioxanthones, oxime esters, etc.

[0254] Examples of the photoinitiator containing an α-hydroxy dimethylacetophenone group include 2-hydroxy-2-methyl-1-phenylpropanone, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-1-methylpropanone, 2-hydroxy-1-(4-(4-(2-hydroxy-2-methylpropanoyl)benzyl)phenyl)-2-methylpropan-1-one, etc.

[0255] Examples of α-hydroxy cycloalkyl ketones include 1-hydroxycyclohexyl phenyl ketone, etc.

[0256] α - aminophenylalkyl ketones include, for example, 2 - methyl - 1 - (4 - methylthiophenyl)-2 - morpholinopropan - 1 - one, etc.

[0257] Benzyl dimethyl ketals include, for example, 2,2 - dimethoxy - 1,2 - diphenylethane - 1 - one, etc.

[0258] Unsubstituted or substituted phenylalkyl ketones 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 - tosyloxy)acetophenone, benzoin, 2 - benzyl - 2 - (dimethylamino)-4'-morpholinobutyrophenone, 2 - methyl - 4'-(methylthio)-2 - morpholinopropiophenone, 2 - isonitroacetophenone, 2,2 - dimethoxy - 1,2 - diphenylethane - 1 - one, etc.

[0259] Unsubstituted or substituted benzyl groups include, for example, benzyl, p - anisyl, etc.

[0260] 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, etc.

[0261] Acylphosphine oxides include, for example, 2,4,6 - trimethylbenzoyl - diphenyl - phosphine oxide, bis(2,4,6 - trimethylbenzoyl)-phenylphosphine oxide, etc.

[0262] Substituted thioxanthones include, for example, 2 - chlorothioxanthone, 2 - isopropylthioxanthone, 2,4 - diethylthioxanthone, etc.

[0263] Oxime esters include, for example, 1,2 - octanedione, 1 - [4 - (phenylthio)-, 2 - (o - benzoyl oxime)] (i.e., 2 - ((benzoyloxy)imino)-1 - (4 - (phenylthio)phenyl)octan - 1 - one);

[0264] Acetone, 1 - [9 - ethyl - 6 - (2 - methylbenzoyl)-9H - carbazol - 3 - yl]-1-(O - acetyl oxime) (i.e., 1 - (((1 - (9 - ethyl - 6 - (2 - methylbenzoyl)-9H - carbazol - 3 - yl)ethylidene)amino)oxy)ethan - 1 - one), etc.

[0265] When electron beam curing is carried out, a photoinitiator is not required.

[0266] In one embodiment, the photoinitiator is preferably selected from acylphosphine oxides. The reasons for the preference can be, for example, fewer precipitates after emulsification, etc.

[0267] The mass% content (photoinitiator / non-volatile content of the active energy ray-curable composition) includes, 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%, etc. In one embodiment, the content is preferably selected from 0 mass% to 30 mass%, and more preferably from 0.1 mass% to 10 mass%.

[0268] <Additive>

[0269] The active energy ray-curable composition may optionally contain an agent (additive) that does not conform to any of the above.

[0270] Examples of additives include organic solvents, antioxidants, ultraviolet absorbers, light stabilizers, defoamers, surface modifiers, antifouling agents, colorants, metal oxide particle dispersions, organic particle dispersions, etc.

[0271] In one embodiment, the mass part content (additive / active energy ray-curable composition) is preferably less than 1 mass part, less than 0.1 mass part, less than 0.01 mass part, 0 mass part, etc.

[0272] In one embodiment, the mass part content (additive / any one of the polymeric anionic emulsifier, poly(meth)acrylate, water, and photoinitiator) is preferably less than 1 mass part, less than 0.1 mass part, less than 0.01 mass part, 0 mass part, etc.

[0273] Examples of the emulsification method include mechanical emulsification method, phase inversion emulsification method, forced emulsification method, reverse emulsification method, high-pressure emulsification method, etc.

[0274] Examples of the emulsification equipment include propeller mixer, turbine mixer, homogenizing mixer, dispersion mixer, super mixer, colloid mill, high-pressure homogenizer, etc.

[0275] Examples of the addition order include the following order, etc.

[0276] (1) Poly(meth)acrylate and, if necessary, photoinitiator, additive

[0277] (2) Polymeric anionic emulsifier

[0278] (3) Water

[0279] In one embodiment, the emulsification temperature is preferably 10°C to 80°C.

[0280] In one embodiment, the emulsification time is preferably 1 minute to 24 hours.

[0281] 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 kneading concentration is preferably selected from 75% by mass to 90% by mass, more preferably from 80% by mass to 90% by mass, and still more preferably from 77% by mass to 86% by mass.

[0282] Examples of the viscosity (active energy ray curable composition) include 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 viscosity is preferably selected from 1000 mPa·s to 500000 mPa·s, and more preferably from 5000 mPa·s to 300000 mPa·s. The reasons for the preference include, for example, improved curability.

[0283] The viscosity can be measured according to the following conditions.

[0284] Measuring machine: VISCOMETER TVK-10, manufactured by Koki Sangyo Co., Ltd.

[0285] Non-volatile content concentration: 15% by mass

[0286] Measuring temperature: 25°C

[0287] Examples of the use (active energy ray curable composition) include coating agents, adhesives, active energy ray curable coating agents, active energy ray curable adhesives, etc.

[0288] [Cured product]

[0289] The present disclosure relates to a cured product of the active energy ray curable composition.

[0290] Examples of the curing conditions include the following conditions, etc.

[0291] [Laminate]

[0292] The present disclosure relates to a laminate comprising the cured product.

[0293] Examples of the manufacturing method (laminate) include the following process methods, etc.

[0294] Coating step: A step of coating the composition on at least one surface of a substrate

[0295] Active energy ray curing step: A step of forming a cured product layer by irradiating active energy rays

[0296] Examples of the base material include a polycarbonate film, an acrylic film (such as a polymethyl methacrylate film), a polystyrene film, a polyester film, a polyolefin film, an epoxy resin film, a melamine resin film, a triacetyl cellulose film, an ABS film, an AS film, a norbornene-based resin film, a cyclic olefin film, a polyvinyl alcohol film, and the like.

[0297] In one embodiment, the thickness (of the base material) is preferably selected from 10 μm to 2000 μm.

[0298] In one embodiment, the thickness (of the cured product layer) is preferably selected from 0.1 μm to 20 μm.

[0299] (Coating step)

[0300] Examples of the coating method include bar coater coating, wire bar coating, Mayer bar coating, air knife coating, gravure coating, reverse gravure coating, flow coater coating, offset printing, flexographic printing, screen printing method, and the like.

[0301] (Active energy ray irradiation step)

[0302] Examples of the active energy rays include ultraviolet rays, electron beams, and the like.

[0303] Examples of the ultraviolet light source include a xenon lamp, a high-pressure mercury lamp, a metal halide lamp, and the like.

[0304] In the case of using a high-pressure mercury lamp, the curing conditions are preferably selected from the following conditions and the like.

[0305] Lamp output: 25 W / cm to 160 W / cm

[0306] UV illuminance: 10 mW / cm 2 to 800 mW / cm 2

[0307] Cumulative light amount: 25 mJ / cm 2 to 2000 mJ / cm 2

[0308] Conveyor speed: 1 m / minute to 50 m / minute

[0309] In the case of using an electron beam, the curing conditions are preferably selected from the following conditions and the like.

[0310] Acceleration voltage: 10 kV to 300 kV

[0311] Conveyor speed: 5 m / minute to 50 m / minute

[0312] [Example]

[0313] Hereinafter, the present invention will be specifically described by way of 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 only limited by the scope of the claims. Unless otherwise specified, values such as parts and % are based on mass.

[0314] Production Example 1: Polymer Anionic Emulsifier

[0315] In a reaction vessel equipped with a thermometer, a stirring device, a condenser, a dropping funnel, and a nitrogen inlet tube, 25.0 parts of itaconic acid, 0.13 parts of sodium methallylsulfonate, 13.2 parts of sodium styrenesulfonate, 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 isopropanol, and 0.5 parts of 2-mercaptoethanol were prepared. While stirring the mixture, it was heated to 50 °C. Then, 2.2 parts of ammonium persulfate (APS) was added and the temperature was raised to 80 °C, and it was stirred for 3 hours. Water was added for cooling to obtain a polymer anionic emulsifier (non-volatile content 25%).

[0316] Unless otherwise specifically mentioned, other examples are changed as shown in the following table, and the rest are carried out in the same manner as described above.

[0317] Production Example 3

[0318] In a reaction vessel equipped with a thermometer, a stirring device, a condenser, a dropping funnel, and a nitrogen inlet tube, while introducing nitrogen, 15 parts of maleic acid, 35 parts of isobutyl alcohol half-ester of maleic acid, and 150 parts of toluene were prepared. Under a nitrogen stream, the reaction system was heated to 110 °C while stirring. Then, 50 parts of styrene was prepared in a dropping funnel, and 5.8 parts of tert-butyl peroxybenzoate and 35 parts of toluene were prepared in another dropping funnel. These were separately dropped into the container over about 1.5 hours, and it was kept warm under reflux for about 2 hours. After that, 2.3 parts of tert-butyl peroxybenzoate and 15 parts of toluene were dropped over about 30 minutes, and it 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 specified amount of water, and 81.6 parts of 28% ammonia water to obtain a polymer anionic emulsifier.

[0319] Production Example 4

[0320] Unless otherwise specified, except for the changes made according to the following table, the other steps of Production Example 4 are the same as those of Production Example 3.

[0321] [Table 1]

[0322]

[0323] MAA: Methacrylic acid

[0324] IA: Itaconic acid

[0325] SMAS: Sodium methallylsulfonate

[0326] NaSS: Sodium styrenesulfonate

[0327] AM: Acrylamide

[0328] HPA: 3 - Hydroxypropyl acrylate

[0329] Man: Maleic acid

[0330] Man - nBu: n - Butyl half - ester of maleic acid

[0331] Man - iBu: Isobutyl half - ester of maleic acid

[0332] Man - EH: 2 - Ethylhexyl half - ester of maleic acid

[0333] Man - Cy: Cyclohexyl half - ester of maleic acid

[0334] MMA: Methyl methacrylate

[0335] 2EHA: 2 - Ethylhexyl acrylate

[0336] CHMA: Cyclohexylmethyl acrylate

[0337] St: Styrene

[0338] The weight - average molecular weight was measured under the following conditions.

[0339] Measuring machine: Manufactured by Tosoh Corporation, GPC (Model: HLC - 8220)

[0340] Chromatographic column: One TSKgel guardcolumnα manufactured by Tosoh Corporation and two TSK - GELα - M (temperature 40°C)

[0341] Detector: TDA MODEL301 manufactured by Viscotek Corporation (concentration detector, 90° light - scattering detector, and viscosity detector (temperature 40°C)), RALLS method

[0342] Eluent: 0.02M NaNO3 / CH3CN = 80 / 20 wt%

[0343] Sample concentration: 0.5 wt%

[0344] Developing temperature: 40°C

[0345] Standard substance: Polyethylene oxide

[0346] Flow rate: 1.0 mL / min

[0347] Sample for measurement: First, the concentration of the sample for measurement was adjusted to 0.5% in terms of the non-volatile content by adding the eluent to prepare the sample for measurement. Then, an aqueous sodium hydroxide solution was added until the pH reached 10 - 12. Then, it was immersed in a hot water bath at 80°C or higher for 1 hour. After that, the pH was adjusted to 6 - 8 with sulfuric acid and diluted to 0.025% with the eluent for measurement.

[0348] Example 1: Actinic energy ray curable composition

[0349] In 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 photoinitiator (2,4,6-trimethylbenzoyl diphenylphosphine oxide) were added, and uniformly stirred at 85°C for 1 hour. After complete dissolution, while maintaining a temperature of 40°C, 3 parts of a high molecular weight anionic emulsifier (Production Example 1), 1 part of a high molecular weight anionic emulsifier (Production Example 2), 1 part of RE-1000L, and 4.7 parts of water were added, and kneaded at 40°C for 1 hour. After that, in order to adjust the non-volatile content, 44.6 parts of water were gradually added for emulsification to obtain an actinic energy ray curable composition (non-volatile content concentration: 50 mass%).

[0350] Unless otherwise specified, other examples are changed as shown in the following table, and the rest is carried out in the same manner as described above.

[0351] [Table 2]

[0352]

[0353]

[0354] 2,4,6-trimethylbenzoyl diphenylphosphine oxide: Product name "Omnirad TPO", manufactured by IGM Resins

[0355] DPHA-40H: Urethane acrylate, product name "KAYARAD DPHA-40H", manufactured by Nippon Kayaku Co., Ltd.

[0356] Miramer M600: Di-pentaerythritol hexaacrylate, product name "Miramer M600", manufactured by Miwon

[0357] RE-1000L: Product name "Amino ion RE-1000L", manufactured by Nippon Emulsion Co., Ltd., ammonium methyl acrylate sulfonate containing a polycyclic phenyl skeleton

[0358] The volume average particle size (D90) was measured under the following conditions.

[0359] Measuring instrument: Microtrac NT 3300 (manufactured by Nikkiso Co., Ltd.)

[0360] Number of measurements: 3

[0361] Measuring temperature: 25 ± 5°C

[0362] Measuring time: 30 seconds

[0363] Particle size classification: standard

[0364] Calculation mode: MT3000II

[0365] Upper limit of measurement: 2000 μm

[0366] Lower limit of measurement: 0.021 μm

[0367] Residue ratio: 0.00%

[0368] Passing ratio: 0.00%

[0369] Residue ratio setting: Inactive particle permeability: Permeable particle shape: Non-spherical

Claims

1. A curable composition for active energy rays, The curable composition for active energy rays contains: Two or more kinds of polymeric anionic emulsifiers, poly(meth)acrylate, and water, The weight average molecular weight of the polymeric anionic emulsifier is 10,000 to 500,000.

2. The curable composition for active energy rays according to claim 1, wherein the two or more kinds of polymeric anionic emulsifiers are selected from the group consisting of polymeric anionic emulsifiers containing (meth)acrylic acid units, polymeric anionic emulsifiers containing itaconic acid units, and polymeric anionic emulsifiers containing maleic acid units.

3. A cured product, which is a cured product of the curable composition for active energy rays according to claim 1 or 2.

4. A laminate, comprising the cured product according to claim 3.

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