Active energy ray curable emulsion composition and coating composition

Abstract

To provide: an active energy ray-curable emulsion composition, which is of forced emulsification type and of high nonvolatile content, has excellent storage stability under normal temperature and high temperature, and provides a coating film having excellent flexibility and adhesion to a substrate; and a coating composition.SOLUTION: Provided is an active energy ray-curable emulsion composition, comprising a photocurable compound (A) and a reactive surfactant (B), where the reactive surfactant (B) comprises a monofunctional reactive surfactant (B1) and a polyfunctional reactive surfactant (B2), and the photocurable compound (A) comprises a urethane (meth)acrylate (A1) (excluding, however, the polyfunctional reactive surfactant (B2)).SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to an active energy ray-curable emulsion composition, particularly an active energy ray-curable emulsion composition obtained by forced emulsification, and a coating agent composition. More specifically, the present invention relates to an emulsion composition and a coating agent composition that exhibit excellent storage stability at room temperature and high temperatures, have a high non-volatile content, and exhibit excellent flexibility and adhesion of the coating film when coated onto a substrate. [Background technology]

[0002] Urethane (meth)acrylates, which are produced by reacting diol compounds such as polyester diols and polyether diols, diisocyanate compounds such as isophorone diisocyanate and diphenylmethane diisocyanate, and hydroxyl group-containing (meth)acrylates such as hydroxyethyl acrylate, are known as active energy ray curable resins and are used in applications such as wood paints and plastic coatings.

[0003] These urethane (meth)acrylates generally have high viscosity. Therefore, when using them, they are diluted with organic solvents or reactive diluents to adjust the viscosity before coating, and then cured by irradiation with active energy rays such as ultraviolet light to form a hardened coating film. However, dilution with organic solvents presents problems under recent VOC regulations concerning air pollution, working environment, and fire hazards. On the other hand, dilution with reactive diluents may require large quantities of the reactive diluent to achieve low viscosity, leading to problems such as difficulty in obtaining sufficient coating film properties.

[0004] Under these circumstances, there has been a growing demand in recent years for water-based systems, such as water-dispersed systems. Patent Document 1 proposes a self-emulsifying, active energy ray-curable resin composition in which a carboxyl group and alkylene glycol chain-containing urethane (meth)acrylate is produced without solvents, the carboxyl groups of the urethane (meth)acrylate are neutralized, and then water is added to emulsify it. Patent Document 2 proposes a forced-emulsification type active energy ray curable aqueous emulsion composition, which is obtained by dispersing a polyfunctional acrylate compound and a photopolymerization initiator in an aqueous medium in the presence of an emulsifier. Patent Document 3 proposes a forced-emulsion type emulsion coating composition obtained by dispersing mono- or polypentaerythritol (meth)acrylate, a urethane poly(meth)acrylate compound, and a photopolymerization initiator in water in the presence of a reactive surfactant. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Japanese Patent Publication No. 2020-152786 [Patent Document 2] Japanese Patent Publication No. 2012-149141 [Patent Document 3] Japanese Patent Application Publication No. 09-137081 [Overview of the Initiative] [Problems that the invention aims to solve]

[0006] However, the technology disclosed in Patent Document 1 has drawbacks in terms of drying properties during coating film formation because, due to its self-emulsifying nature, it is difficult to achieve high non-volatile differentiation while maintaining low viscosity. Furthermore, the storage stability of the liquid at high temperatures is not considered. Moreover, the flexibility of the coating film is not considered.

[0007] Furthermore, in the technology disclosed in Patent Document 2, forced emulsification is performed using a non-reactive emulsifier in the examples. When an emulsion composition obtained using such a non-reactive emulsifier is formed into a cured coating film, the non-reactive emulsifier remains in a free state, resulting in insufficient water resistance. Although examples of reactive emulsifiers are given in the text, the above point is not considered at all. Moreover, the flexibility of the coating film is not considered.

[0008] Furthermore, while the technology disclosed in Patent Document 3 uses a reactive emulsifier for forced emulsification, it does not consider the storage stability of the liquid at high temperatures. It also does not consider the flexibility of the cured coating film.

[0009] Against this backdrop, the present invention aims to provide an active energy ray curable emulsion composition and a coating composition that are forced-emulsified, have a high non-volatile content, exhibit excellent storage stability at room temperature and high temperatures, and also have excellent flexibility of the coating film and adhesion to the substrate. [Means for solving the problem]

[0010] In view of these circumstances, the inventors conducted extensive research and, as a result, discovered that by combining urethane (meth)acrylate (A1) with a specific surfactant, an active energy ray curable emulsion composition can be obtained that exhibits excellent storage stability at room temperature and high temperatures, has a high non-volatile content, and provides excellent flexibility and adhesion of the coating film when applied to a substrate. Thus, the present invention was completed.

[0011] The present invention has the following aspects. [1] An active energy ray curable emulsion composition comprising a photopolymerizable compound (A) and a reactive surfactant (B), wherein the reactive surfactant (B) comprises a monofunctional reactive surfactant (B1) and a polyfunctional reactive surfactant (B2), and the photopolymerizable compound (A) comprises a urethane (meth)acrylate (A1) (excluding the polyfunctional reactive surfactant (B2)). [2] The active energy ray curable emulsion composition according to [1], wherein the urethane (meth)acrylate (A1) is a reaction product of polyisocyanate (a1), at least one selected from polyester polyol (a2-1) and polyether polyol (a2-2), and hydroxyl group-containing (meth)acrylate (a3). [3] The active energy ray curable emulsion composition according to [2], wherein at least one selected from the polyester polyol (a2-1) and polyether polyol (a2-2) has a number average molecular weight of 300 to 10,000. [4] The active energy ray curable emulsion composition according to [2] or [3], wherein the polyester polyol (a2-1) contains a component derived from at least one of isophthalic acid and an ester-forming derivative of isophthalic acid. [5] The active energy ray curable emulsion composition according to any one of [2] to [4], wherein the hydroxyl group-containing (meth)acrylate (a3) ​​comprises a polyoxyalkylene chain-containing compound. [6] The active energy ray curable emulsion composition according to any one of [1] to [5], wherein the content of the photopolymerizable compound (A) is 40 to 99% by weight with respect to 100% by weight of the total of the photopolymerizable compound (A), the monofunctional reactive surfactant (B1), and the polyfunctional reactive surfactant (B2). [7] The active energy ray curable emulsion composition according to any one of [1] to [6], wherein the monofunctional reactive surfactant (B1) is a surfactant represented by the following general formula (1). XO-(Y1O) m -(Y2O) n -SO3Z ···(1) (However, X is a functional group containing a double bond. Y1 and Y2 are independently alkylene groups, m is an integer greater than or equal to 1, n is an integer greater than or equal to 0, and Y1 and Y2 are different groups. Z represents the counterion.) [8] The active energy ray curable emulsion composition according to any one of [1] to [7], wherein the polyfunctional reactive surfactant (B2) has a polyoxyalkylene chain. [9] The active energy ray curable emulsion composition according to any one of [1] to [8], wherein the polyfunctional reactive surfactant (B2) is urethane (meth)acrylate.

[10] Furthermore, an active energy ray curable emulsion composition according to any one of [1] to [9], comprising a photopolymerization initiator (C).

[11] A coating agent composition comprising the active energy ray-curable emulsion composition according to any one of [1] to

[10] .

Advantages of the Invention

[0012] According to the present invention, there are provided an active energy ray-curable emulsion composition which is a forced emulsification type, has a high non-volatile content, is excellent in storage stability at room temperature and high temperature, and is also excellent in flexibility of the coating film and adhesion to the substrate, and a coating composition.

Embodiments for Carrying Out the Invention

[0013] The present invention will be described in detail below. In the present invention, “(meth)acryl” means acrylic or methacrylic, “(meth)acryloyl” means acryloyl or methacryloyl, and “(meth)acrylate” means acrylate or methacrylate, respectively. The number average molecular weight is the number average molecular weight in terms of standard polystyrene molecular weight, and is measured, for example, by a method based on the hydroxyl value measured in accordance with JIS K 1577 or by high performance liquid chromatography. In high performance liquid chromatography, for example, it is measured by using four columns in series: ACQUITY APC XT 450×1, ACQUITY APC XT 200×1, ACQUITY APC XT 45×2 on a high performance liquid chromatograph (manufactured by Waters, “ACQUITY APC system”). The weight average molecular weight is the weight average molecular weight in terms of standard polystyrene molecular weight, and is measured, for example, by using four columns in series: ACQUITY APC XT 450×1, ACQUITY APC XT 200×1, ACQUITY APC XT 45×2 on a high performance liquid chromatograph (manufactured by Waters, “ACQUITY APC system”).

[0014] The active energy ray-curable emulsion composition of the present invention is an active energy ray-curable emulsion composition containing a photopolymerizable compound (A) and a reactive surfactant (B) (hereinafter, also simply referred to as "emulsion composition").

[0015] <Photopolymerizable compound (A)> The photopolymerizable compound (A) includes urethane (meth)acrylate (A1) (however, excluding the polyfunctional reactive surfactant (B2)). Urethane (meth)acrylate (A1) is water-insoluble and non-water-dispersible. "Water-insoluble and non-water-dispersible" means not fitting both the definitions of "water-soluble" and "water-dispersible" described later. Examples of urethane (meth)acrylate (A1) include reaction products of polyisocyanate, polyol, and hydroxyl group-containing (meth)acrylate, and reaction products of polyisocyanate and hydroxyl group-containing (meth)acrylate. Among these, reaction products of polyisocyanate, polyol, and hydroxyl group-containing (meth)acrylate are preferred because a flexible coating film can be obtained. As urethane (meth)acrylate (A1), from the viewpoint of coating film toughness, a reaction product of polyisocyanate (a1), at least one selected from polyester polyol (a2-1) and polyether polyol (a2-2), and hydroxyl group-containing (meth)acrylate (a3) is particularly preferred.

[0016] 〔Polyisocyanate (a1)〕 Examples of polyisocyanate (a1) include aromatic polyisocyanate, aliphatic polyisocyanate, alicyclic polyisocyanate, or trimer compounds or higher multimer compounds of these polyisocyanates, allophanate-type polyisocyanate, biuret-type polyisocyanate, and water-dispersible polyisocyanate. Examples of aromatic polyisocyanates include tolylene diisocyanate, diphenylmethane diisocyanate, polyphenylmethane polyisocyanate, modified diphenylmethane diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, phenylene diisocyanate, and naphthalene diisocyanate. Examples of aliphatic polyisocyanates include pentamethylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, and lysine triisocyanate. Examples of alicyclic polyisocyanates include hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, and norbornene diisocyanate. These polyisocyanates (a1) may be used individually or in combination of two or more types.

[0017] Among these, aliphatic diisocyanates such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, and lysine diisocyanate, and alicyclic diisocyanates such as hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, and norvonene diisocyanate are preferred in that they cause less yellowing, and more preferably isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, and hydrogenated xylylene diisocyanate, and even more preferably isophorone diisocyanate and hydrogenated xylylene diisocyanate in that they have excellent flexibility and low crystallinity of the coating film.

[0018] [Polyester polyol (a2-1)] The polyester polyol (a2-1) is preferably at least one selected from the group consisting of a condensation polymer of a polyhydric alcohol and a polyhydric carboxylic acid, a ring-opening polymer of a cyclic ester compound, and a reaction product of three components: a polyhydric alcohol, a polyhydric carboxylic acid, and a cyclic ester compound. From the viewpoint of compositional flexibility, a condensation polymer of a polyhydric alcohol and a polyhydric carboxylic acid is particularly preferred.

[0019] The polyhydric alcohol may be a dihydric alcohol or a trihydric or higher alcohol. Examples of dihydric alcohols include aliphatic diols, alicyclic diols, and aromatic diols. Examples of aliphatic diols include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, trimethylene glycol, 1,4-tetramethylenediol, 1,3-tetramethylenediol, 2-methyl-1,3-trimethylenediol, 1,5-pentamethylenediol, neopentyl glycol, 1,6-hexamethylenediol, 3-methyl-1,5-pentamethylenediol, and 2,4-diethyl-1,5-pentamethylenediol. Examples of alicyclic diols include 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, spiroglycol, tricyclodecanedimethanol, adamantanediol, and 2,2,4,4-tetramethyl-1,3-cyclobutanediol. Examples of aromatic diols include bisphenols (bisphenol A, bisphenol B, bisphenol E, etc.), 4,4'-thiodiphenol, 4,4'-methylenediphenol, 4,4'-dihydroxybiphenyl, o-dihydroxybenzene, m-dihydroxybenzene, p-dihydroxybenzene, 2,5-naphthalenediol, p-xylenediol, and their ethylene oxide adducts and propylene oxide adducts. Examples of alcohols with a hydride of three or higher include glycerin, trimethylolpropane, trimethylolethane, and sugar alcohols (such as xylitol and sorbitol). These polyhydric alcohols may be used individually or in combination of two or more.

[0020] Among these, dihydric alcohols are preferred, and aliphatic diols are preferred from the viewpoint of flexibility of the coating film, and more preferably ethylene glycol, 1,6-hexamethylenediol, 1,5-pentamethylenediol, 1,4-tetramethylenediol, 3-methyl-1,5-pentamethylenediol, and 2-methyl-1,3-trimethylenediol.

[0021] Examples of polycarboxylic acids include aliphatic dicarboxylic acids, alicyclic dicarboxylic acids, aromatic dicarboxylic acids, trivalent or higher aromatic carboxylic acids, and ester-forming derivatives of these polycarboxylic acids. Examples of aliphatic dicarboxylic acids include malonic acid, maleic acid, fumaric acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, and dodecanedionic acid. Examples of alicyclic dicarboxylic acids include 1,3-cyclopentanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, and 1,4-cyclohexanedicarboxylic acid. Examples of aromatic dicarboxylic acids include terephthalic acid, isophthalic acid, orthophthalic acid, 2,6-naphthalenedicarboxylic acid, and p-phenylenedicarboxylic acid. Examples of trivalent or higher aromatic carboxylic acids include trimellitic acid, pyromellitic acid, and trimesic acid. Ester-forming derivatives of polycarboxylic acids are compounds derived from polycarboxylic acids that can form esters upon reaction with polyhydric alcohols. Examples include carboxylate salts, carboxylic acid anhydrides, carboxylic acid halides, and carboxylic acid esters. These polycarboxylic acids may be used individually or in combination of two or more.

[0022] As for polycarboxylic acids, aliphatic dicarboxylic acids, aromatic dicarboxylic acids, and their ester-forming derivatives are preferred from the viewpoint of contributing to adhesion to the substrate, adipic acid, isophthalic acid, terephthalic acid, and their ester-forming derivatives are more preferred, adipic acid, isophthalic acid, and their ester-forming derivatives are even more preferred from the viewpoint of flexibility of the coating film, and isophthalic acid and its ester-forming derivatives are particularly preferred. The polyester polyol (a2-1) preferably contains components derived from at least one of isophthalic acid and an ester-forming derivative of isophthalic acid.

[0023] Examples of cyclic ester compounds include propiolactone, β-methyl-δ-valerolactone, and ε-caprolactone. These cyclic ester compounds may be used individually or in combination of two or more.

[0024] The method for producing polyester polyol (a2-1) is not particularly limited. For example, polyester polyol (a2-1) can be obtained by charging a mixture of a polyhydric alcohol and a polycarboxylic acid and a catalyst into a reactor, heating it to, for example, 150-260°C, and allowing the esterification or transesterification reaction to proceed while distilling off by-products such as water or methanol. Alternatively, a cyclic ester compound may be used instead of the mixture of a polyhydric alcohol and a polycarboxylic acid, or both the mixture of a polyhydric alcohol and a polycarboxylic acid and a cyclic ester compound may be used. Furthermore, an esterifying derivative of a polycarboxylic acid may be used instead of the polycarboxylic acid, or in addition to the polycarboxylic acid.

[0025] [Polyether polyol (a2-2)] Examples of polyether polyols (a2-2) include polyalkylene glycols having an oxyalkylene structure such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polybutylene glycol, and polyhexamethylene glycol, as well as linear polyether polyols such as random or block copolymers of these polyalkylene glycols, and polyether polyols containing a branched structure (a structure including branched polyether chains) made from trivalent or higher alcohols such as glycerin and trimethylolpropane, or trivalent or higher amines such as ethylenediamine. The above can be used individually or in combination of two or more types.

[0026] Among these, linear polyether polyols are preferred, and polytetramethylene ether glycol and polypropylene glycol are even more preferred, with polytetramethylene ether glycol being particularly preferred from the viewpoint of coating film toughness.

[0027] If the polyester polyol (a2-1) or polyether polyol (a2-2) has too many hydroxyl groups, gelation tends to occur more easily during the reaction. The number of hydroxyl groups in the polyester polyol (a2-1) or polyether polyol (a2-2) is preferably 2 to 5, more preferably 2 to 3, and particularly preferably 2, from the viewpoint of excellent flexibility of the coating film and adhesion to the substrate.

[0028] The number average molecular weight of the polyester polyol (a2-1) or polyether polyol (a2-2) is preferably 300 to 10,000, more preferably 350 to 5,000, and even more preferably 400 to 2,500. If the number average molecular weight of the polyester polyol (a2-1) or polyether polyol (a2-2) is above the lower limit of the above range, the flexibility and adhesion of the coating film to the substrate are improved. If the number average molecular weight of the polyester polyol (a2-1) or polyether polyol (a2-2) is below the upper limit of the above range, the curability is improved.

[0029] [Hydroxyl group-containing (meth)acrylate (a3)] The ethylenically unsaturated groups in the hydroxyl group-containing (meth)acrylate (a3) ​​may be one, two, or three or more. Examples of hydroxyl group-containing (meth)acrylates having one ethylenically unsaturated group include hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and 6-hydroxyhexyl (meth)acrylate, as well as 2-hydroxyethyl acryloyl phosphate, 2-(meth)acryloyloxyethyl-2-hydroxypropyl phthalate, caprolactone-modified 2-hydroxyethyl (meth)acrylate, dipropylene glycol (meth)acrylate, fatty acid-modified glycidyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, and 2-hydroxy-3-(meth)acryloyloxypropyl (meth)acrylate. Examples of hydroxyl group-containing (meth)acrylates having two ethylenically unsaturated groups include glycerin di(meth)acrylate and 2-hydroxy-3-acryloyl-oxypropyl methacrylate. Examples of hydroxyl group-containing (meth)acrylates having three or more ethylenically unsaturated groups include pentaerythritol tri(meth)acrylate, caprolactone-modified pentaerythritol tri(meth)acrylate, ethylene oxide-modified pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, caprolactone-modified dipentaerythritol penta(meth)acrylate, and ethylene oxide-modified dipentaerythritol penta(meth)acrylate. These hydroxyl group-containing (meth)acrylates (a3) ​​may be used individually or in combination of two or more types.

[0030] Among these, hydroxyl group-containing (meth)acrylates containing one ethylenically unsaturated group are preferred, and from the viewpoint of the balance between hydrophilicity and lipophilicity, hydroxyalkyl (meth)acrylates with 2 to 4 carbon atoms such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, and polypropylene glycol mono(meth)acrylate are more preferred, and 2-hydroxyethyl (meth)acrylate and polyethylene glycol mono(meth)acrylate are even more preferred. The hydroxyl group-containing (meth)acrylate (a3) ​​preferably contains a polyoxyalkylene chain-containing compound. The alkylene group of the polyoxyalkylene chain is preferably an alkylene group having 2 to 4 carbon atoms. Polyethylene glycol mono(meth)acrylate is particularly preferred as the polyoxyalkylene chain-containing compound included in the hydroxyl group-containing (meth)acrylate (a3).

[0031] The urethane (meth)acrylate (A1) may be a reaction product obtained by further reacting at least one selected from polyisocyanate (a1), polyester polyol (a2-1), and polyether polyol (a2-2), and a hydroxyl group-containing (meth)acrylate (a3), with other components. For example, polyethylene glycol, carboxyl group-containing polyols, etc., may be used as other components to adjust hydrophilicity. As the carboxyl group-containing polyol, an aliphatic polyhydroxycarboxylic acid is preferred, more preferably a diol monocarboxylic acid or its neutralized salt having a molecular weight of 100 to 200, particularly preferably dimethylolbutanoic acid, dimethylolpropionic acid, and even more preferably dimethylolbutanoic acid. The carboxyl groups derived from the carboxyl group-containing polyol are partially or completely neutralized by a base, becoming hydrophilic by forming a neutralized salt.

[0032] Urethane (meth)acrylate (A1) does not have self-emulsifying properties. However, it is preferable to introduce a moderate amount of hydrophilic groups to facilitate emulsification by a reactive surfactant (B).

[0033] The acid value of urethane (meth)acrylate (A1) is preferably 40 mg KOH / g or less, more preferably 25 mg KOH / g or less, and particularly preferably 10 mg KOH / g or less. If the acid value of the above urethane (meth)acrylate (A1) is too high, it becomes highly viscous and difficult to handle, and the emulsion stability decreases. The above acid value can be determined by a method in accordance with JIS K 0070.

[0034] The weight-average molecular weight of urethane (meth)acrylate (A1) is preferably 1,000 to 100,000, more preferably 1,500 to 50,000, and even more preferably 2,000 to 20,000. If the weight-average molecular weight of urethane (meth)acrylate (A1) is above the lower limit of the above range, the flexibility and adhesion of the coating film are improved. If the weight-average molecular weight of urethane (meth)acrylate (A1) is below the upper limit of the above range, the emulsifying properties and emulsion stability are excellent.

[0035] The viscosity of urethane (meth)acrylate (A1) at 60°C is preferably 500 to 1,000,000 mPa·s, more preferably 1,000 to 500,000 mPa·s, and even more preferably 2,000 to 100,000 mPa·s. If the viscosity of urethane (meth)acrylate (A1) is within the above range, it exhibits excellent handling properties. Viscosity is measured using an E-type viscometer.

[0036] The method for producing urethane (meth)acrylate (A1) is not particularly limited, and examples include the following methods (i) to (iii), with method (ii) being preferred in terms of reaction stability and reduction of by-products. (i) A method of reacting polyisocyanate (a1), polyester polyol (a2-1) or polyether polyol (a2-2), and hydroxyl group-containing (meth)acrylate (a3) ​​by charging them together or separately into a reactor. (ii) A method of reacting a hydroxyl group-containing (meth)acrylate (a3) ​​with a reaction product obtained by first reacting a polyisocyanate (a1) with a polyester polyol (a2-1) or a polyether polyol (a2-2). (iii) A method of reacting a reaction product obtained by pre-reacting a polyisocyanate (a1) with a hydroxyl group-containing (meth)acrylate (a3) ​​with a polyester polyol (a2-1) or a polyether polyol (a2-2). In methods (i) to (iii), urethane (meth)acrylate (A1) is obtained by terminating the reaction when the residual isocyanate group content in the reaction system becomes 0.5% by weight or less.

[0037] In methods (i) to (iii), it is preferable to use a catalyst to accelerate the reaction. Examples of such catalysts include organometallic compounds, metal salts, amine catalysts, bismuth catalysts, zirconium catalysts, and zinc 2-ethylhexanoate / zirconium tetraacetylacetonate. Examples of organometallic compounds include dibutyltin dilaurate, trimethyltin hydroxide, tetra-n-butyltin, and tin octoate. Examples of metal salts include zinc octenoate, tin octenoate, cobalt naphthenate, stannous chloride, and stannous chloride. Examples of amine catalysts include triethylamine, benzyldiethylamine, 1,4-diazabicyclo[2,2,2]octane, 1,8-diazabicyclo[5,4,0]undecene, N,N,N',N'-tetramethyl-1,3-butanediamine, and N-ethylmorpholine. Examples of bismuth-based catalysts include bismuth nitrate, bismuth bromide, bismuth iodide, bismuth sulfide, as well as organic bismuth compounds such as dibutylbismuth dilaurate and dioctylbismuth dilaurate, and organic bismuth acid salts such as bismuth 2-ethylhexanoate, bismuth naphthenate, bismuth isodecanate, bismuth neodecanoate, bismuth laurate, bismuth maleate, bismuth stearate, bismuth oleate, bismuth linoleate, bismuth acetate, bismuth lybisneodecanoate, bismuth disalicylate, and bismuth digallate. Examples of zirconium-based catalysts include inorganic zirconium, organozirconium, and elemental zirconium. Among these, dibutyltin dilaurate and 1,8-diazabicyclo[5,4,0]undecene are particularly preferred. These catalysts may be used individually or in combination of two or more.

[0038] In methods (i) to (iii), organic solvents that do not have functional groups that react with isocyanate groups can be used, such as esters like ethyl acetate and butyl acetate, ketones like methyl ethyl ketone and methyl isobutyl ketone, and aromatics like toluene and xylene. From the viewpoint of reducing environmental impact, it is preferable to carry out the reaction without a solvent.

[0039] The reaction temperature can be 30 to 90°C, preferably 40 to 80°C. The reaction time can be 2 to 10 hours, preferably 3 to 8 hours.

[0040] The proportion of urethane (meth)acrylate (A1) in 100% by weight of photopolymerizable compound (A) is preferably 5 to 100% by weight, more preferably 20 to 100% by weight, even more preferably 50 to 95% by weight, and particularly preferably 70 to 90% by weight. When the proportion of urethane (meth)acrylate (A1) is within the above range, an excellent balance between emulsion stability and coating film flexibility is obtained.

[0041] The photopolymerizable compound (A) may optionally further contain other photopolymerizable compounds other than urethane (meth)acrylate (A1). Examples of other photopolymerizable compounds include (meth)acrylic monomer, acrylic (meth)acrylate, polyester (meth)acrylate, and polyether (meth)acrylate. When phase-inversion emulsification of high-viscosity compounds such as urethane acrylate without solvents, it is preferable to use low-viscosity compounds such as (meth)acrylic monomer in combination. Low-viscosity compounds such as (meth)acrylic monomer may be added during the production of urethane (meth)acrylate (A1), in which case the compound acts as a diluent.

[0042] Examples of (meth)acrylic monomers include monofunctional (meth)acrylate monomers, difunctional (meth)acrylate monomers, and trifunctional or more (meth)acrylate monomers. Examples of monofunctional (meth)acrylate monomers include methyl (meth)acrylate, ethyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, phenoxyethyl (meth)acrylate, 2-phenoxy-2-hydroxypropyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, 3-chloro-2-hydroxypropyl (meth)acrylate, glycerin mono(meth)acrylate, glycidyl (meth)acrylate, lauryl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, tricyclodecanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, dicyclopentenyl Ntanyl (meth)acrylate, (2-methyl-2-ethyl-1,3-dioxolan-4-yl)-methyl (meth)acrylate, cyclohexanespiro-2-(1,3-dioxolan-4-yl)-methyl (meth)acrylate, cyclic trimethylolpropane formal acrylate, 3-ethyl-3-oxetanyl methyl (meth)acrylate, γ-butyrolactone (meth)acrylate, n-butyl (meth)acrylate, hexyl (meth)acrylate )Acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, dodecyl (meth)acrylate, n-stearyl (meth)acrylate, benzyl (meth)acrylate, phenoxydiethylene glycol acrylate, phenoxypolyethylene glycol acrylate, nonylphenol propylene oxide modified (n=2.5) Examples of phthalic acid derivatives such as (meth)acrylate, 2-(meth)acryloyloxyethyl acid phosphate, 2-(meth)acryloyloxy-2-hydroxypropyl phthalate, half-(meth)acrylate, furfuryl(meth)acrylate, tetrahydrofurfuryl(meth)acrylate, carbitol(meth)acrylate, butoxyethyl(meth)acrylate, (meth)acryloylmorpholine, allyl(meth)acrylate, and polyoxyethylene secondary alkyl ether acrylate can be cited.

[0043] Examples of difunctional (meth)acrylate monomers include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, and ethylene oxide. Examples include modified bisphenol A type di(meth)acrylate, propylene oxide modified bisphenol A type di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,6-hexanediol ethylene oxide modified di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, diglycidyl phthalate di(meth)acrylate, hydroxypivalic acid modified neopentyl glycol di(meth)acrylate, and 2-(meth)acryloyloxyethyl acid phosphate diester.

[0044] Examples of (meth)acrylate monomers with three or more functions include trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tri(meth)acryloyloxyethoxytrimethylolpropane, isocyanurate ethylene oxide-modified triacrylate, ethylene oxide-modified dipentaerythritol hexa(meth)acrylate, ethylene oxide-modified pentaerythritol tetra(meth)acrylate, caprolactone-modified dipentaerythritol hexa(meth)acrylate, and caprolactone-modified pentaerythritol tetra(meth)acrylate. (Meth)acrylic monomers may be used alone or in combination of two or more.

[0045] Among these, monofunctional (meth)acrylate monomers are preferred as (meth)acrylic monomers due to their excellent flexibility of the coating film, and phenoxyethyl (meth)acrylate, phenoxydiethylene glycol acrylate, phenoxypolyethylene glycol acrylate, tetrahydrofurfuryl (meth)acrylate, (meth)acryloylmorpholine, polyoxyethylene secondary alkyl ether acrylate, and isobornyl (meth)acrylate are more preferred due to their excellent emulsifying properties and flexibility, with phenoxydiethylene glycol acrylate, phenoxypolyethylene glycol acrylate, and isobornyl (meth)acrylate being particularly preferred.

[0046] The viscosity of the photopolymerizable compound (A) at 60°C can be 10 to 500,000 mPa·s, preferably 100 to 200,000 mPa·s, more preferably 200 to 100,000 mPa·s, and even more preferably 500 to 50,000 mPa·s. If the viscosity of the photopolymerizable compound (A) is above the lower limit of the above range, the need to reduce its viscosity by forced emulsification increases. If the viscosity of the photopolymerizable compound (A) is below the upper limit of the above range, it becomes easier to apply shear force, improving emulsification properties and emulsion stability.

[0047] <Reactive surfactant (B)> Reactive surfactants (B) include monofunctional reactive surfactants (B1) and polyfunctional reactive surfactants (B2).

[0048] [Monofunctional reactive surfactant (B1)] Monofunctional reactive surfactants (B1) are essential components for obtaining small-particle, uniform emulsions. Such monofunctional reactive surfactants are those that contain one radical-reactive unsaturated bond in their molecule.

[0049] Monofunctional reactive surfactant (B1) is a surfactant having one functional group with a double bond. Preferably, such a functional group is a (meth)acryloyl group or an allyl group. The monofunctional reactive surfactant (B1) preferably has a linear structure, and more preferably has a linear polyoxyalkylene chain. The alkylene group of the linear polyoxyalkylene chain is preferably an alkylene group having 2 to 4 carbon atoms. It is even more preferable that the monofunctional reactive surfactant (B1) has a linear polyoxyalkylene chain in which one end is a functional group having a double bond and the other end is a hydrophilic group. The hydrophilic group is preferably an ionic group (cationic, anionic, or amphoteric), more preferably an anionic group, and particularly preferably a sulfonic acid base.

[0050] As the monofunctional reactive surfactant (B1), a monofunctional reactive surfactant represented by the following general formula (1) is preferred because it yields an emulsion composition with smaller particle size and greater uniformity. XO-(Y1O) m -(Y2O) n -SO3Z ···(1) (However, X is a functional group containing a double bond. Y1 and Y2 are independently alkylene groups, m is an integer greater than or equal to 1, n is an integer greater than or equal to 0, and Y1 and Y2 are different groups. Z represents the counterion.)

[0051] The functional group having a double bond in X is preferably a (meth)acryloyl group or an allyl group. Y1 and Y2 are preferably alkylene groups having 2 to 4 carbon atoms. m is preferably 2 or more, more preferably 3 or more. The upper limit of m is preferably 30 or less, more preferably 20 or less, and even more preferably 10 or less. n is preferably 1 or more, more preferably 2 or more. The upper limit of n is preferably 30 or less, more preferably 20 or less, and even more preferably 10 or less. For Z, NH is preferred. 4+ kaNa + And, particularly preferably NH 4+ That is the case.

[0052] Examples of monofunctional reactive surfactants (B1) include (meth)acrylate surfactants, allyl surfactants, maleic acid surfactants, and itaconic acid surfactants. Specifically, examples include sodium sulfoethyl methacrylate, ammonium sulfoethyl methacrylate, allyl group-containing polyoxyethylene nonylphenyl ether sulfonate, polyoxyethylene lauryl ether maleate, polyoxyethylene lauryl ether methacrylate, polyoxyethylene nonylphenyl ether acrylic acid, and allyl group-containing polyoxyethylene nonylphenyl ether. These may be used individually or in combination of two or more.

[0053] <Multifunctional reactive surfactant (B2)> In this invention, by using not only a monofunctional reactive surfactant (B1) but also a polyfunctional reactive surfactant (B2) in combination, an emulsion composition with small particle size and uniformity can be obtained. The polyfunctional reactive surfactant (B2) not only assists in emulsification but also greatly contributes to the stability after emulsification, particularly freeze-thaw stability. Polyfunctional reactive surfactants (B2) are either water-soluble or water-dispersible. "Water-soluble" means that a uniform appearance can be maintained when prepared as a 10% by weight aqueous solution. "Water-dispersible" means that when prepared as a 10% by weight aqueous dispersion, particles are dispersed with a median diameter of less than 100 nm. The particle size (median diameter) is measured using a laser scattering / diffraction device (Horiba, Ltd.; LA950V2).

[0054] A polyfunctional reactive surfactant (B2) is a surfactant having two or more functional groups having double bonds. Preferably, such functional groups are (meth)acryloyl groups and allyl groups. The main chain structure of a polyfunctional reactive surfactant (B2) is not limited as long as it has two or more functional groups having double bonds and a hydrophilic structure. Specifically, examples include polyvinyl alcohol, acrylic (meth)acrylate, urethane (meth)acrylate, polyester (meth)acrylate, and polyether (meth)acrylate, all of which have two or more functional groups having double bonds. Among these, urethane (meth)acrylate, which is water-soluble or water-dispersible and has two or more functional groups having double bonds, is preferred due to the hydrophilic nature of the urethane bonds and the ease of molecular design control.

[0055] The polyfunctional reactive surfactant (B2) preferably has a hydrophilic group in its molecule. The hydrophilic group is preferably a nonionic group, more preferably a polyoxyalkylene chain, and even more preferably a polyoxyethylene chain. Examples of urethane (meth)acrylates that satisfy these conditions include reaction products of polyisocyanate (b1), hydroxyl group-containing (meth)acrylate (b2), and polyoxyethylene group-containing compound (b3). Also, examples include reaction products of polyisocyanate (b1), hydroxyl group-containing (meth)acrylate (b2), polyoxyethylene group-containing compound (b3), and carboxyl group-containing polyol (b4), in which some or all of the carboxyl groups are neutralized by a base. As polyisocyanate (b1), the same compounds exemplified in polyisocyanate (a1) can be used as examples. Examples of hydroxyl group-containing (meth)acrylates (b2) include those compounds exemplified in hydroxyl group-containing (meth)acrylates (a3) ​​that have two ethylenically unsaturated groups, and those exemplified as hydroxyl group-containing (meth)acrylates that have three or more ethylenically unsaturated groups. Polyethylene glycol can be cited as an example of a polyoxyethylene group-containing compound (b3). Examples of carboxyl group-containing polyols (b4) include the same compounds as the carboxyl group-containing polyols exemplified in urethane (meth)acrylate (A1).

[0056] The weight-average molecular weight of the polyfunctional reactive surfactant (B2) is preferably 500 to 50,000, and more preferably 1,000 to 20,000. If the weight-average molecular weight of the polyfunctional reactive surfactant (B2) is above the lower limit of the above range, the cured coating film is less likely to become brittle. If the weight-average molecular weight of the polyfunctional reactive surfactant (B2) is below the upper limit of the above range, it will have a moderate viscosity, making it easy to handle, and the hardness of the cured coating film will be improved.

[0057] <Photopolymerization initiator (C)> The emulsion composition of the present invention preferably contains a photopolymerization initiator (C) in order to promote curing when irradiated with active energy rays. One type of photopolymerization initiator (C) may be used alone, or two or more types may be used in combination.

[0058] The photopolymerization initiator (C) is not particularly limited as long as it generates radicals upon the action of light, for example, 2,2-dimethoxy-1,2-diphenylethane-1-one, 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 1-(4-isopropylenephenyl)-2-hydroxy-2-methylpropane-1-one, 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropane-1-one, 4-(2-hydroxyethoxy)-phenyl(2-hydroxy-2-propyl)ketone, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1-one, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyldimethyl ketal, benzophenone, benzoyl Benzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3'-dimethyl-4-methoxybenzophenone, thioxanthone, 2-chlorthioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, camphorquinone, dibenzosverone, 2-ethylanthraquinone, 4',4''-diethylisophthalophenone, 3,3 Examples include ',4,4'-tetra(t-butylperoxycarbonyl)benzophenone, α-acyloxime ester, acylphosphine oxide, methylphenylglyoxylate, benzyl, 9,10-phenanthylenequinone, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)ketone, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide. In particular, benzyldimethyl ketal, 1-hydroxycyclohexylphenyl ketone, benzoin isopropyl ether, 4-(2-hydroxyethoxy)-phenyl(2-hydroxy-2-propyl) ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide are preferred, with 1-hydroxycyclohexylphenyl ketone (IGM Resins, "Omnirad 184"), 2-hydroxy-2-methyl-1-phenylpropan-1-one (IGM Resins, "Omnirad 1173"), and 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one (IGM Resins' "Omnirad 907" and 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (IGM Resins' "Omnirad TPO") are particularly preferred.

[0059] As the photopolymerization initiator (C), it is preferable to use a photopolymerization initiator that is water-soluble or water-dispersible, in order to further enhance the functionality of the composition in terms of its application as an aqueous dispersion. Examples of such photopolymerization initiators (C) include 2-(3-dimethylamino-2-hydroxypropoxy)-3,4-dimethyl-9H-thioxanthon-9-one metochloride (Octel Chemicals, "Quantacure QTX"), 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one (IGM Resins, "Omnirad 2959"), IGM Resins, "ESACURE DP250", and Fujifilm Wako Pure Chemical Industries, Ltd., "FOM-03011". These may be used individually or in combination of two or more. Among these, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one (IGM Resins, "Omnirad 2959") is particularly preferred.

[0060] The timing of adding the photopolymerization initiator (C) is not particularly limited; it may be forcibly emulsified together with the photopolymerizable compound (A), etc., or added to the emulsion composition after forcibly emulsifying. However, in the case of a non-water-soluble and solid photopolymerization initiator, forcibly emulsifying it together with the photopolymerizable compound (A), etc., is preferable from the viewpoint of the appearance of the coating film.

[0061] The content of the photopolymerizable compound (A) in the emulsion composition of the present invention is preferably 40 to 99% by weight, more preferably 50 to 95% by weight, even more preferably 60 to 90% by weight, and particularly preferably 70 to 80% by weight, based on 100% by weight of the total of the photopolymerizable compound (A), monofunctional reactive surfactant (B1), and polyfunctional reactive surfactant (B2). If the content of the photopolymerizable compound (A) is above the lower limit of the above range, the physical properties derived from the photopolymerizable compound (A) are more easily exhibited, and hardness and water resistance are improved. If the content of the photopolymerizable compound (A) is below the upper limit of the above range, the relative amount of reactive surfactant necessary to emulsify the photopolymerizable compound (A) is less likely to be insufficient, and emulsification and emulsion stability are improved.

[0062] The content of the polyfunctional reactive surfactant (B1) in the emulsion composition of the present invention is preferably 0.1 to 20% by weight, more preferably 1.0 to 10% by weight, even more preferably 1.5 to 7.0% by weight, and particularly preferably 2.0 to 5.0% by weight, based on 100% by weight of the total of the photopolymerizable compound (A), monofunctional reactive surfactant (B1), and polyfunctional reactive surfactant (B2). If the content of the polyfunctional reactive surfactant (B1) is above the lower limit of the above range, the emulsion tends to have small particle sizes and a sharp particle size distribution, improving storage stability, especially storage stability at high temperatures. If the content of the polyfunctional reactive surfactant (B1) is below the upper limit of the above range, the physical properties derived from the photopolymerizable compound (A) are easily exhibited, improving the flexibility, adhesion, and water resistance of the coating film.

[0063] The content of the polyfunctional reactive surfactant (B2) in the emulsion composition of the present invention is preferably 0.9 to 59.9% by weight, more preferably 4.0 to 49% by weight, even more preferably 8.5 to 38.5% by weight, and particularly preferably 18 to 25% by weight, based on 100% by weight of the total of the photopolymerizable compound (A), monofunctional reactive surfactant (B1), and polyfunctional reactive surfactant (B2). If the content of the polyfunctional reactive surfactant (B2) is above the lower limit of the above range, the emulsion will have small particle sizes and a sharp particle size distribution, improving storage stability, especially freeze-thaw stability. If the content of the polyfunctional reactive surfactant (B2) is below the upper limit of the above range, the physical properties derived from the photopolymerizable compound (A) will be fully exhibited, improving the flexibility, adhesion, and water resistance of the coating film.

[0064] The amount of photopolymerization initiator (C) used is preferably 1 to 20 parts by weight, more preferably 1 to 16 parts by weight, and particularly preferably 2 to 10 parts by weight, per 100 parts by weight of the total of the photopolymerizable compound (A), monofunctional reactive surfactant (B1), and polyfunctional reactive surfactant (B2). If the amount of photopolymerization initiator (C) used is above the lower limit of the above range, the curing rate by irradiation with active energy rays such as ultraviolet light becomes sufficiently fast, and the desired cured coating film is easily obtained. Even if the amount of photopolymerization initiator (C) used exceeds the upper limit of the above range, the curability does not improve, and by keeping it below the upper limit of the above range, the cured coating film is less likely to yellow.

[0065] The emulsion composition of the present invention may further contain any components other than the photopolymerizable compound (A), monofunctional reactive surfactant (B1), and polyfunctional reactive surfactant (B2), as long as they do not impede the effects of the present invention. Examples of optional components include surface modifiers (leveling agents), UV absorbers, organic fillers, inorganic fillers, dyes and pigments, oils, plasticizers, waxes, drying agents, dispersants, wetting agents, gelling agents, stabilizers, defoamers, thixotropy-imparting agents, antioxidants, tackifiers, flame retardants, antistatic agents, fillers, reinforcing agents, matting agents, crosslinking agents, silica, water-dispersed silica, preservatives, fungicides, freeze-thaw stabilizers (ethylene glycol, etc.), film-forming agents (butyl cellosolve, etc.), and polar solvents for water dispersion assistance (N-methylpyrrolidone, 3-methoxy-N,N-dimethylpropionamide, etc.). These may be used individually or in combination of two or more. Furthermore, aqueous dispersions or aqueous solutions of acrylic emulsions, polyurethane dispersions, or other materials different from the emulsion composition of the present invention may be incorporated. These components may be forcibly emulsified together with the photopolymerizable compound (A), etc., or added to the emulsion composition after forcibly emulsifying.

[0066] The non-volatile content concentration of the emulsion composition of the present invention is preferably 5 to 80% by weight, more preferably 10 to 70% by weight, and even more preferably 20 to 60% by weight, based on 100% by weight of the total mass of the emulsion composition of the present invention, from the viewpoint of coating workability. If the non-volatile content concentration is above the lower limit of the above range, repelling from the substrate during coating is less likely to occur, and the drying load is reduced. If the non-volatile content concentration is below the upper limit of the above range, the fluidity is improved, and coating becomes easier.

[0067] The average core particle diameter of the emulsion composition of the present invention is preferably 10 to 1,000 nm, more preferably 50 to 500 nm, even more preferably 60 to 200 nm, and particularly preferably 70 to 150 nm. If the average core particle diameter is above the lower limit of the above range, the emulsion viscosity becomes sufficiently low, resulting in excellent handling properties. If the average core particle diameter is below the upper limit of the above range, aggregation is less likely to occur, and emulsification stability is improved. The average core particle diameter refers to the average value of the scattering intensity distribution on a volume basis. The core particle diameter is measured using a laser scattering and diffraction device (Horiba, Ltd.; LA950V2).

[0068] The viscosity of the emulsion composition of the present invention at 25°C is preferably 5 to 20,000 mPa·s, more preferably 10 to 10,000 mPa·s, and even more preferably 20 to 5,000 mPa·s. If the viscosity is above the lower limit of the above range, film thickness control becomes easier. If the viscosity is below the upper limit of the above range, it becomes easier to handle and the coating workability is improved. The viscosity is measured using an E-type viscometer (100 rpm).

[0069] <Method for manufacturing emulsion> Next, a method for producing the active energy ray curable emulsion composition of the present invention will be described. The emulsion composition of the present invention is obtained by forcibly emulsifying a photopolymerizable compound (A) in an aqueous solvent by a phase inversion emulsification method using a monofunctional reactive surfactant (B1) and a polyfunctional reactive surfactant (B2). "Forced emulsification" is a method of emulsifying and dispersing a compound that is insoluble in water and does not have emulsifying power on its own in an aqueous solvent using a surfactant and shear force. A commonly known method involves adding organic solvents such as methyl ethyl ketone or acetone to reduce viscosity during phase inversion emulsification, followed by desolvent removal under reduced pressure after emulsification is complete. The system of the present invention can also employ such a method. However, from the viewpoint of VOC reduction, a method of performing phase inversion emulsification without solvents is preferred.

[0070] As a specific method, for example, a photopolymerizable compound (A), a monofunctional reactive surfactant (B1), and a polyfunctional reactive surfactant (B2) are added to a beaker container, and then deionized water is gradually added while stirring at 40-70°C using a stirrer such as a high-speed disperser, double-cylinder homogenizer, ultrasonic homogenizer, blender, or mixer. When the added deionized water exceeds a certain amount, a phase inversion occurs from water-in-oil (W / O) to oil-in-water (O / W), and the strong stirring force applied during the phase inversion yields a small-particle, uniform emulsion composition. After that, stirring is continued until it returns to room temperature, and the desired emulsion composition is obtained by adding and mixing surface modifiers, defoamers, preservatives, antifungal agents, photopolymerization initiators, etc., as needed. The emulsion composition of the present invention, for example, as an emulsion composition with a concentration of 50% by weight, can maintain a uniform dispersion state without precipitation even after being left to stand at room temperature (23°C) for 1 to 2 months.

[0071] The aqueous solvent is not limited to water; it may also be a solvent prepared by mixing water with a lower alcohol having 1 to 5 carbon atoms, etc., as long as it does not impair the emulsified state. The amount of aqueous solvent used is preferably 5 to 80% by weight, more preferably 10 to 70% by weight, and even more preferably 20 to 60% by weight, based on 100% by weight of the total mass of the emulsion composition of the present invention. If the amount of aqueous solvent used is above the lower limit of the above range, phase inversion is likely to occur, and the viscosity is likely to become sufficiently low. If the amount of aqueous solvent used is below the upper limit of the above range, the drying load during coating will be reduced.

[0072] As described above, the emulsion composition of the present invention contains a photopolymerizable compound (A) containing urethane (meth)acrylate (A1), a monofunctional reactive surfactant (B1), and a polyfunctional reactive surfactant (B2). The inclusion of urethane (meth)acrylate (A1) in the photopolymerizable compound (A) results in a coating film with excellent flexibility and adhesion. Furthermore, by forcibly emulsifying the photopolymerizable compound (A) using the monofunctional reactive surfactant (B1) and the polyfunctional reactive surfactant (B2) in combination, a uniform emulsion composition with small particle size can be obtained. Therefore, the obtained emulsion composition has excellent storage stability at room temperature and high temperatures. In particular, using an anionic monofunctional reactive surfactant (B1) provides an electrostatic repulsion effect between particles, while using a nonionic urethane acrylate as a polyfunctional reactive surfactant (B2) provides a steric repulsion effect between particles. When these are used in combination, the synergistic effect of both strengthens the repulsion between particles, resulting in an emulsion composition with very small and uniform particle sizes compared to when each reactive surfactant is used alone.

[0073] The emulsion composition of the present invention is not particularly limited in its applications and is extremely useful as a film-forming material for various purposes, such as paints, protective coatings, anchor coatings, hard coat coatings, inks, magnetic powder coating binders, sandblasting films, adhesives, viscous adhesives, and printing plates.

[0074] <Coating agent composition> The emulsion composition of the present invention can be used, for example, as a coating agent composition (curable resin composition) for forming a coating film on various substrates, and is useful as a topcoat agent, anchor coat agent, etc. For example, the emulsion composition of the present invention can be coated onto a substrate, dried, and then irradiated with active energy rays to harden the coating film and form a cured coating film on the substrate.

[0075] Examples of coating methods include wet coating methods such as spraying, showering, dipping, rolling, spinning, and screen printing. The drying temperature can be 40 to 120°C, preferably 50 to 100°C. The drying time can be 1 to 20 minutes, preferably 2 to 10 minutes.

[0076] Examples of active energy rays include far-ultraviolet, ultraviolet, near-ultraviolet, and infrared rays, as well as electromagnetic waves such as X-rays and gamma rays, and electron beams, proton beams, and neutron beams. Among these, ultraviolet irradiation is preferred due to its curing speed, availability of irradiation equipment, and cost. When electron beam irradiation is performed, the coating agent composition of the present invention can be cured without using a photopolymerization initiator (C).

[0077] Methods for curing coatings using ultraviolet irradiation include, for example, using high-pressure mercury lamps, ultra-high-pressure mercury lamps, carbon arc lamps, metal halide lamps, xenon lamps, chemical lamps, LED lamps, etc., that emit light in the wavelength range of 150 to 450 nm. The ultraviolet irradiation dose is 100 to 3000 mJ / cm². 2 This should be sufficient. After UV irradiation, heating may be performed as needed to ensure proper curing.

[0078] Examples of substrates for forming a cured coating include molded products (films, sheets, cups, etc.) made of resins such as polyolefins (polyethylene, polypropylene, polycyclopentadiene, etc.), polycarbonate, polyester, ABS resin, and acrylic resin, as well as metals and glass. [Examples]

[0079] The present invention will be specifically described below with reference to examples, but the present invention is not limited to the following description. In the examples, "parts" and "%" refer to weight-based values.

[0080] <Name and structure of photopolymerizable compound (A)> • (A-1): Phenoxydiethylene glycol acrylate (Product name: Light Acrylate P2H-A; manufactured by Kyoeisha Chemical Co., Ltd.) • (A-2): Dipentaerythritol acrylic acid adduct with a hydroxyl value of 51 mgKOH / g (Product name: KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.) • (A-3): Acryloylmorpholine (Product name: ACMO; manufactured by KJ Chemicals) • (A-4): Isobornyl acrylate (Product name: IBXA; manufactured by Osaka Organic Chemical Industry Co., Ltd.)

[0081] <Monofunctional reactive surfactant (B1)> • (B1-1): Ammonium polyoxyalkylene alkenyl ether sulfate (product name: Latemul PD-104; manufactured by Kao Corporation); corresponds to the above general formula (1)

[0082] <Photopolymerization initiator (C)> • (C-1): 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one (product name: Omnirad 2959; manufactured by IGM Resins)

[0083] Prior to the examples, the following urethane (meth)acrylate (A1) and urethane acrylate as a polyfunctional reactive surfactant (B2) were prepared.

[0084] <Preparation of urethane (meth)acrylate (A1)> [Manufacturing of urethane acrylate (A1-1)] In a flask equipped with an internal thermometer, stirrer, and condenser, 123 g (0.554 mol) of isophorone diisocyanate, 555 g (0.277 mol) of a polyester polyol compound [linear structure, bifunctional; polycarboxylic acid component: adipic acid; polyhydric alcohol components: ethylene glycol, 1,4-tetramethylenediol; hydroxyl value 56.0 mg KOH / g; number average molecular weight calculated from hydroxyl value 2,004], 1.00 g of 2,6-di-tert-butylcresol as a polymerization inhibitor, and 0.1 g of dibutyltin dilaurate as a reaction catalyst were added, and the mixture was reacted at 60°C. When the remaining isocyanate groups were 3.4% or less, 322 g (0.568 mol) of polyethylene glycol monoacrylate [hydroxyl value: 99.0 mg KOH / g, weight-average molecular weight calculated from the hydroxyl value: 567] was added and the reaction was carried out at 60°C. The reaction was terminated when the remaining isocyanate groups were 0.1% or less, and a composition containing urethane acrylate (A1-1) was obtained (resin concentration: 100%, weight-average molecular weight: 13,100, viscosity: 14,500 mPa·s / 60°C).

[0085] [Manufacturing of urethane acrylate (A1-2)] In a flask equipped with an internal thermometer, stirrer, and condenser, 207 g (0.930 mol) of isophorone diisocyanate, 431 g (0.465 mol) of a polyester polyol compound [linear structure, bifunctional; polycarboxylic acid component: adipic acid, isophthalic acid; polyhydric alcohol component: 1,6-hexamethylenediol; hydroxyl value 121 mg KOH / g; number average molecular weight calculated from hydroxyl value 927], 0.4 g of 2,6-di-tert-butylcresol as a polymerization inhibitor, and 0.1 g of dibutyltin dilaurate as a reaction catalyst were added, and the mixture was reacted at 60°C. When the remaining isocyanate groups were 6.1% or less, 319 g (0.581 mol) of polyethylene glycol monoacrylate [hydroxyl value: 102 mg KOH / g, weight-average molecular weight calculated from the hydroxyl value: 548] and 43.2 g (0.372 mol) of 2-hydroxyethyl acrylate were added and reacted at 60°C. The reaction was terminated when the remaining isocyanate groups were 0.1% or less to obtain a composition containing urethane acrylate (A1-2) (resin concentration: 100%, weight-average molecular weight: 6,700, viscosity: 7,500 mPa·s / 60°C).

[0086] [Manufacturing of urethane acrylate (A1-3)] In a flask equipped with an internal thermometer, stirrer, and condenser, 180 g (0.812 mol) of isophorone diisocyanate, 431 g (0.406 mol) of a polyester polyol compound [linear structure, bifunctional; polycarboxylic acid component: adipic acid, isophthalic acid; polyhydric alcohol component: 3-methyl-1,5-pentamethylenediol; hydroxyl value 62 mg KOH / g; number average molecular weight calculated from hydroxyl value 1810], 0.4 g of 2,6-di-tert-butylcresol as a polymerization inhibitor, and 0.1 g of dibutyltin dilaurate as a reaction catalyst were added, and the mixture was reacted at 70°C. When the remaining isocyanate group content was 3.7% or less, 18.0 g (0.122 mol) of dimethylolbutanate was added, and the mixture was reacted at 95°C. When the remaining isocyanate groups were 2.6% or less, 68.3 g (0.588 mol) of 2-hydroxyethyl acrylate was added and the reaction was carried out at 70°C. The reaction was terminated when the remaining isocyanate groups were 0.1% or less to obtain a composition containing urethane acrylate (A1-3) (resin concentration: 100%, weight-average molecular weight: 12,000, viscosity: 4,800 mPa·s / 60°C, acid value: 6.8 mg KOH / g).

[0087] [Manufacturing of urethane acrylate (A1-4)] In a flask equipped with an internal thermometer, stirrer, and condenser, 265 g (1.19 mol) of isophorone diisocyanate, 604 g (0.597 mol) of a polyether polyol compound [linear structure, bifunctional; hydroxyl value 111 mg KOH / g; number average molecular weight calculated from hydroxyl value 10¹⁰; product name: BioPTMG1000; manufactured by Mitsubishi Chemical Corporation], 0.4 g of 2,6-di-tert-butylcresol as a polymerization inhibitor, and 0.1 g of dibutyltin dilaurate as a reaction catalyst were added, and the mixture was reacted at 60°C. When the remaining isocyanate group content was 5.8% or less, 17.7 g (0.119 mol) of dimethylolbutanoic acid was added, and the mixture was reacted at 95°C. When the remaining isocyanate groups were 4.5% or less, 113 g (0.973 mol) of 2-hydroxyethyl acrylate was added and the reaction was carried out at 60°C. The reaction was terminated when the remaining isocyanate groups were 0.1% or less, yielding a composition containing urethane acrylate (A1-4) (resin concentration: 100%, viscosity: 17,100 mPa·s / 60°C, acid value: 6.7 mg KOH / g).

[0088] [Manufacturing of urethane acrylate (A1-5)] In a flask equipped with an internal thermometer, stirrer, and condenser, 169 g (0.759 mol) of isophorone diisocyanate, 751 g (0.380 mol) of a polyether polyol compound [linear structure, bifunctional; hydroxyl value 56.7 mg KOH / g; number average molecular weight calculated from hydroxyl value 1980; product name: BioPTMG2000; manufactured by Mitsubishi Chemical Corporation], 0.4 g of 2,6-di-tert-butylcresol as a polymerization inhibitor, and 0.1 g of dibutyltin dilaurate as a reaction catalyst were added, and the mixture was reacted at 60°C. When the remaining isocyanate group content was 3.5% or less, 18.0 g (0.121 mol) of dimethylolbutanate was added, and the mixture was reacted at 95°C. When the remaining isocyanate groups were 2.3% or less, 62.1 g (0.535 mol) of 2-hydroxyethyl acrylate was added and the reaction was carried out at 60°C. The reaction was terminated when the remaining isocyanate groups were 0.1% or less, yielding a composition containing urethane acrylate (A1-5) (resin concentration: 100%, viscosity: 43,700 mPa·s / 60°C, acid value: 6.8 mg KOH / g).

[0089] <Preparation of polyfunctional reactive surfactant (B2)> [Manufacturing of urethane acrylate (B2-1)] In a flask equipped with an internal thermometer, stirrer, and condenser, 96.1 g (0.432 mol) of isophorone diisocyanate, 606 g (0.519 mol) of dipentaerythritol acrylic adduct [hydroxyl value: 48.0 mg KOH / g], 1.65 g of 2,6-di-tert-butylcresol as a polymerization inhibitor, and 0.1 g of dibutyltin dilaurate as a reaction catalyst were added, and the mixture was reacted at 70°C. When the remaining isocyanate groups were 2.1% or less, the mixture was cooled to 60°C, and 298 g (0.302 mol) of polyethylene glycol [hydroxyl value: 114.0 mg KOH / g, weight-average molecular weight calculated from the hydroxyl value: 984] was added. The reaction was carried out at 60°C, and the reaction was terminated when the remaining isocyanate groups were 0.1% or less to obtain a composition containing urethane acrylate (B2-1) (resin concentration: 100%, weight-average molecular weight: 3500, viscosity: 1200 mPa·s / 60°C).

[0090] [Manufacturing of urethane acrylate (B2-2)] In a flask equipped with an internal thermometer, stirrer, and condenser, 529 g (0.378 mol, product name: E402-100; manufactured by Asahi Kasei Corporation), 87.7 g (0.756 mol) of hexamethylene diisocyanate-based polyisocyanate, 1.00 g of 2,6-di-tert-butylcresol as a polymerization inhibitor, and 0.1 g of dibutyltin dilaurate as a reaction catalyst were added, and the mixture was reacted at 60°C. When the remaining isocyanate groups were 2.6% or less, the mixture was cooled to 60°C, and 383 g (0.379 mol) of polyethylene glycol [hydroxyl value: 114.0 mg KOH / g, weight-average molecular weight calculated from the hydroxyl value: 984] was added. The reaction was carried out at 60°C, and the reaction was terminated when the remaining isocyanate groups were 0.1% or less to obtain a composition containing urethane acrylate (B2-2) (resin concentration: 100%, weight-average molecular weight: 8,600, viscosity: 2,700 mPa·s / 60°C).

[0091] [Manufacturing of urethane acrylate (B2-3)] In a flask equipped with an internal thermometer, stirrer, and condenser, 318 g (0.547 mol) of hexamethylene diisocyanate trimer compound, 127 g (1.10 mol) of 2-hydroxyethyl acrylate, 1.00 g of 2,6-di-tert-butyl cresol as a polymerization inhibitor, and 0.1 g of dibutyltin dilaurate as a reaction catalyst were added, and the mixture was reacted at 60°C. When the remaining isocyanate groups were 5.2% or less, the mixture was cooled to 60°C, and 555 g (0.564 mol) of polyethylene glycol [hydroxyl value: 114.0 mg KOH / g, weight-average molecular weight calculated from the hydroxyl value: 984] was added. The reaction was carried out at 60°C, and the reaction was terminated when the remaining isocyanate groups were 0.1% or less to obtain a composition containing urethane acrylate (B2-3) (resin concentration: 100%, weight-average molecular weight: 6,100, viscosity: 1,500 mPa·s / 60°C).

[0092] <Preparation of dispersion> [Example 1] In a cylindrical container, urethane acrylate (A2-1), photopolymerizable compound (A-1), and urethane acrylate (B2-1) were added. After heating and holding at 60°C, monofunctional reactive surfactant (B1-1) was added, and purified water at 50°C was added while stirring with a disperser. Finally, the mixture was stirred while returning to room temperature to prepare an active energy ray curable emulsion composition (50% non-volatile content). The composition of the mixture is shown in Table 1.

[0093] [Examples 2 and 3 and Comparative Examples 1-3] An active energy ray-curable emulsion composition (50% non-volatile content) was prepared in the same manner as in Example 1, except that the formulation was changed as shown in Table 1.

[0094] [Examples 7-14] An active energy ray-curable emulsion composition (50% non-volatile content) was prepared in the same manner as in Example 1, except that the formulation was changed as shown in Table 3.

[0095] <Rating> The active energy ray curable emulsion compositions obtained in each example were evaluated as follows.

[0096] [25℃ viscosity] The viscosity of the 50% non-volatile active energy ray curable emulsion compositions prepared in Examples 1-3, 7-14, and Comparative Example 1 was measured at 25°C using an E-type viscometer (100 rpm).

[0097] [Average core particle diameter] For the active energy ray curable emulsion compositions with 50% non-volatile content prepared in Examples 1-3, 7-14, and Comparative Examples 1-3, the average core particle diameter (volume-based average diameter) was measured using a laser scattering / diffraction device (Horiba, Ltd.; LA950V2).

[0098] [Storage stability at room temperature] The active energy ray-curable emulsion compositions with 50% non-volatile content prepared in Examples 1-3, 7-14, and Comparative Examples 1-3 were placed in containers with lids, and the number of days they could be stored at room temperature (25°C) was visually evaluated as follows. (Evaluation Criteria) ◎: No separation or sedimentation after more than 2 months. ○: No separation or sedimentation after 1 week to less than 2 months. △: No separation or precipitation after 3 days to less than 1 week. ×: Separation and sedimentation in 2 days or less

[0099] [Storage stability at 40°C] The active energy ray-curable emulsion compositions with 50% non-volatile content prepared in Examples 1-3 and Comparative Example 1 were placed in containers with lids and left to stand at 40°C for one week, and then at 40°C for two weeks. The appearance of the liquid and particle size were observed and evaluated according to the following criteria. (Evaluation Criteria) ◎: No increase in particle size ○: Slight increase in particle size (increase of less than 100 nm) △: Increased particle size (increase of 100 nm or more) ×: Separation and precipitation or particle size greater than 1000 nm

[0100] [Examples 4-6 and Comparative Example 4] Using the active energy ray-curable emulsion compositions with a nonvolatile content of 50% obtained in Examples 1 to 3 and Comparative Example 1, coating film samples were prepared by the method described below and evaluated.

[0101] 〔Examples 15 to 20〕 Using the active energy ray-curable emulsion compositions with a nonvolatile content of 50% obtained in Examples 7 to 12, coating film samples were prepared by the method described below and evaluated.

[0102] 〔Preparation of Coating Film Samples for Evaluation〕 Based on 100 parts by weight of the solid content of the active energy ray-curable emulsion compositions with a nonvolatile content of 50% obtained in Examples 1 to 3, 7 to 12 and Comparative Example 1, a photopolymerization initiator (C-1) and a surface conditioner (product name: TegoWet 270; manufactured by Evonik Japan Co., Ltd.) were stirred and mixed as shown in Table 2. This was coated on an easily adherent polyethylene terephthalate (PET) film (manufactured by Toyobo Co., Ltd.; Cosmo Shine A4360, thickness 125 μm), an acrylonitrile-butadiene-styrene copolymer synthetic resin (ABS) white board (manufactured by Nippon Test Panel Co., Ltd.) or a polycarbonate (PC) board (manufactured by Nippon Test Panel Co., Ltd.) using a bar coater, dried at 100 °C for 2 minutes, and then irradiated with ultraviolet rays using a high-pressure mercury lamp so that the integrated light amount became 1,000 mJ / cm 2 to cure the active energy ray-curable emulsion composition, and a coating film sample for evaluation with a film thickness of 10 μm was prepared. The following evaluations were performed using the obtained coating film samples for evaluation.

[0103] 〔Appearance of Coating Film〕 The surface state of the coating film sample for evaluation was observed and evaluated according to the following criteria. (Evaluation Criteria) ◎: No peeling is observed. ○: Almost no peeling is observed. ×: Coating film defects such as peeling and bumps are observed.

[0104] 〔Pencil Hardness〕 Using the evaluation coating samples coated on the above-mentioned easy-adhesion PET film, the pencil hardness was measured under a 750g load according to the method of JIS K 5600-5-4.

[0105] [Flexibility] The flexibility of the evaluation coating samples was evaluated using a cylindrical mandrel bending tester in accordance with JIS K 5600-5-1. The maximum diameter (integer value, mm) at which cracking or peeling occurred when the evaluation coating sample was wrapped around a test rod was measured and evaluated as follows. (Evaluation Criteria) ◎: Less than 2 (No cracking occurs even with a diameter of 2 mm) ○: 2~3 △: 4~5 ×: 6 or more

[0106] [ABS adhesion] An adhesion test was performed using 1mm cross-cut grid-like adhesion samples coated on an ABS whiteboard, and the adhesion between the cured coating and the ABS board was evaluated as follows. (Evaluation Criteria) ○: 91 / 100 or more (Number of remaining items (number of squares without peeling or chipping) / Number of items measured) △: 80 / 100 or more, 90 / 100 or less ×: 79 / 100 or less

[0107] [PC adhesion] An adhesion test was performed using 1 mm cross-cut grid-like adhesion samples coated on PC boards, and the adhesion between the cured coating and the PC board was evaluated as follows. (Evaluation Criteria) ○: 91 / 100 or more (Number of remaining items (number of squares without peeling or chipping) / Number of items measured) △: 80 / 100 or more, 90 / 100 or less ×: 79 / 100 or less

[0108] [Preparation of coating samples for elongation evaluation] Each component was mixed according to the solid content ratios of Examples 1-3, 7-12, and Comparative Example 1 in Tables 1 and 3. Four parts of 1-hydroxycyclohexylphenyl ketone (IGM Resins, "Omnirad 184") were added as a photopolymerization initiator to 100 parts of the solid content of the mixture, and the mixture was diluted with ethyl acetate to a solid content of 70% to prepare an active energy ray-curable composition. The prepared active energy ray-curable composition was coated onto a release polyethylene terephthalate (PET) film (100 μm thick) using an applicator, dried at 60°C for 30 minutes, and then exposed to a high-pressure mercury lamp at an integrated light intensity of 1,000 mJ / cm². 2 The active energy ray curable composition was cured by irradiating it with ultraviolet light to produce an evaluation coating sample with a thickness of 100 μm. Next, this evaluation coating sample was punched out with a dumbbell to produce strip-shaped samples with a width of 15 mm and a length of 75 mm. After that, the cured coating was peeled off the PET film to obtain a coating sample for elongation evaluation.

[0109] [Elongation] For the coating film samples used for elongation evaluation, tensile tests were conducted using a tensile testing machine "AG-X" (manufactured by Shimadzu Corporation) at a temperature of 23°C and 50% humidity, in accordance with JIS K 7127. The tensile speed was 10 mm / min, and the elongation at the fracture point of the coating film was measured and evaluated according to the following criteria. ○···20% or more ×···Less than 20%

[0110] The evaluation results for each example are shown in Tables 1 to 4.

[0111] [Table 1]

[0112] [Table 2]

[0113] [Table 3]

[0114] [Table 4]

[0115] As shown in Tables 1 to 4, the emulsion compositions of Examples 1 to 3 and 7 to 14, in which the photopolymerizable compound (A) was forcibly emulsified with a monofunctional reactive surfactant (B1) and a polyfunctional reactive surfactant (B2), were smaller in particle size, more uniform, and exhibited superior storage stability at room temperature and 40°C compared to the emulsion compositions of Comparative Examples 1 to 3. Furthermore, the coating films of Examples 4 to 6 and 15 to 20, using the emulsion compositions of Examples 1 to 3 and 7 to 12, exhibited superior flexibility and adhesion to the substrate compared to the coating film of Comparative Example 4, which used the emulsion composition of Comparative Example 1. [Industrial applicability]

[0116] The active energy ray curable emulsion composition of the present invention has excellent storage stability at room temperature and high temperatures, and also exhibits excellent flexibility and adhesion of the coating film. Therefore, it is extremely useful as a coating-forming material for various applications, such as paints, adhesives, glues, viscous adhesives, inks, protective coatings, anchor coatings, hard coat coatings, magnetic powder coating binders, sandblasting films, printing plates, coatings for optical film topcoats, metal vapor deposition and sputtering films, and coatings for glass modification.

Claims

1. An active energy ray curable emulsion composition containing a photopolymerizable compound (A) and a reactive surfactant (B), The reactive surfactant (B) comprises a monofunctional reactive surfactant (B1) and a polyfunctional reactive surfactant (B2), The photopolymerizable compound (A) comprises urethane (meth)acrylate (A1) (excluding the polyfunctional reactive surfactant (B2)), The urethane (meth)acrylate (A1) is a reaction product of polyisocyanate (a1), at least one selected from polyester polyol (a2-1) and polyether polyol (a2-2), and hydroxyl group-containing (meth)acrylate (a3). An active energy ray curable emulsion composition in which the monofunctional reactive surfactant (B1) is a surfactant represented by the following general formula (1). XO-(Y1O) m-(Y2O)n-SO3Z...(1) (However, X is a functional group having a double bond. Y1 and Y2 are independently alkylene groups, m is an integer greater than or equal to 1, n is an integer greater than or equal to 0, and Y1 and Y2 are different groups. Z represents the counterion.)

2. The activated energy ray curable emulsion composition according to claim 1, wherein at least one selected from the polyester polyol (a2-1) and polyether polyol (a2-2) has a number average molecular weight of 300 to 10,000.

3. The active energy ray curable emulsion composition according to claim 1, wherein the polyester polyol (a2-1) contains a component derived from at least one of isophthalic acid and an ester-forming derivative of isophthalic acid.

4. The active energy ray curable emulsion composition according to claim 1, wherein the hydroxyl group-containing (meth)acrylate (a3) ​​contains a polyoxyalkylene chain-containing compound.

5. The active energy ray curable emulsion composition according to claim 1, wherein the content of the photopolymerizable compound (A) is 40 to 99% by weight based on 100% by weight of the total of the photopolymerizable compound (A), the monofunctional reactive surfactant (B1), and the polyfunctional reactive surfactant (B2).

6. The active energy ray curable emulsion composition according to claim 1, wherein the polyfunctional reactive surfactant (B2) has a polyoxyalkylene chain.

7. The active energy ray curable emulsion composition according to claim 1, wherein the polyfunctional reactive surfactant (B2) is urethane (meth)acrylate.

8. Furthermore, the active energy ray curable emulsion composition according to claim 1, further comprising a photopolymerization initiator (C).

9. A coating agent composition comprising the active energy ray curable emulsion composition according to any one of claims 1 to 8.

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