JP2023038939A - Aqueous emulsion composition, release coating agent, cured material, and laminate - Google Patents

Abstract

To provide an aqueous emulsion composition which exhibits such effects as suppression of an amount of silicone migration, light releasability, and the like.SOLUTION: Provided is an aqueous emulsion composition, comprising a (meth)acrylate (A) which comprises one or more selected from the group consisting of a polysiloxane (A1) having a (meth)acryloyloxy group on the side chain and a reaction product (A2) of components including a polysiloxane (a1) having a hydroxyl group, a (meth)acrylate (a2) having a hydroxyl group, polyethylene glycol (a3) having a hydroxyl group at one end, and a tri- or more functional isocyanate (a4).SELECTED DRAWING: None

Description

TECHNICAL FIELD The present disclosure relates to aqueous emulsion compositions, release coating agents, cured products, and laminates.

Plastic films such as polyethylene terephthalate are used in various industrial fields due to their excellent performance such as transparency, dimensional stability, mechanical properties and chemical resistance. Specifically, for example, it can be used as a base film for optical film products such as a prism sheet for LCD members, a light diffusion sheet, a reflector, an antireflection plate, a touch panel, an explosion-proof film, and a PDP filter.

In addition, plastic films are often used as base films for release films, and are also used as separators for various adhesive sheets, protective films for touch panels, and the like.

As a release coating agent used for a release film, a coating agent containing a silicone resin is known, and particularly when an organo-modified polysiloxane is used, the releasability tends to be improved. However, the silicone resin often bleeds out on the surface of the coating film and migrates to adherends such as pressure-sensitive adhesives and resin moldings laminated on the coating film, resulting in deterioration of the properties thereof.

Patent Literature 1 proposes a method of laminating a mixture of an acrylic resin, a melamine resin and a silicone resin. However, the above compound liquid requires a temperature of 190° C. for curing, and causes great thermal damage to the substrate. In addition, as described in Patent Document 2, an acid catalyst may be used in combination for the purpose of improving the curability of the melamine resin. In some cases, the workability was deteriorated.

JP-A-11-170440 JP-A-2002-19037

The problem to be solved by the present disclosure is to provide an aqueous emulsion composition that exhibits effects such as suppression of the amount of silicone migration and easy release properties.

As a result of extensive studies, the inventors have found that the above problems can be solved by using a given compound.

The following items are provided by this disclosure.
(Item 1)
Polysiloxane (A1) having a (meth)acryloyloxy group in a side chain, polysiloxane (a1) having a hydroxyl group, (meth)acrylate having a hydroxyl group (a2), polyethylene glycol having a hydroxyl group at one end (a3) and 3 An aqueous emulsion composition containing a (meth)acrylate (A) containing at least one selected from the group consisting of reactants (A2) of components containing a functional or higher polyisocyanate (a4).
(Item 2)
Item 1. The water-based emulsion according to Item 1, which contains a urethane (meth)acrylate (B) that is a reaction product of a component containing a hydroxyl group-containing (meth)acrylate (b1), a hydroxyl group-containing polyethylene glycol (b2), and a polyisocyanate (b3). Composition.
(Item 3)
3. The aqueous emulsion composition according to Item 1 or 2, containing one or more (C) selected from polyfunctional (meth)acrylate (c1) and polyfunctional (meth)acrylamide (c2).
(Item 4)
4. The aqueous emulsion composition according to any one of items 1 to 3, which contains a photopolymerization initiator (D).
(Item 5)
5. The aqueous emulsion composition according to any one of items 1 to 4, which contains an organic diluent (E).
(Item 6)
A release coating agent comprising the aqueous emulsion composition according to any one of Items 1 to 5.
(Item 7)
A cured product of the aqueous emulsion composition according to any one of items 1 to 5 or the release coating agent according to item 6.
(Item 8)
A laminate comprising the cured product according to item 7 and a substrate.

The water-based emulsion composition provided by the present disclosure exhibits effects such as suppression of the amount of silicone migration and easy peelability.

Throughout the present disclosure, the range of numerical values for each physical property value, content, etc. can be set as appropriate (for example, by selecting from the upper and lower limit values described in each item below). Specifically, for the numerical value α, when A1, A2, A3, etc. are exemplified as the lower limit of the numerical value α, and B1, B2, B3, etc. are exemplified as the upper limit of the numerical value α, the range of the numerical value α is A1 or more, A2 or more, A3 or more, B1 or less, B2 or less, B3 or less, A1-B1, A1-B2, A1-B3, A2-B1, A2-B2, A2-B3, A3-B1, A3-B2, A3-B3 etc. are exemplified. In the present disclosure, "~" is used to mean including the numerical values before and after it as lower and upper limits.

<(A) Component>
Polysiloxane (A1) having a (meth)acryloyloxy group in the side chain of the present disclosure (also referred to as "(A1) component" in the present disclosure) and polysiloxane (a1) having a hydroxyl group (in the present disclosure, "( a1) component”), (meth)acrylate having a hydroxyl group (a2) (also referred to as “(a2) component” in the present disclosure), polyethylene glycol having a hydroxyl group at one end (a3) (in the present disclosure , Also referred to as "(a3) component") and tri- or higher functional polyisocyanate (a4) (also referred to as "(a4) component" in the present disclosure). Reactant (A2) (in the present disclosure, (Also referred to as "(A2) component") containing (meth)acrylate (A) (also referred to as "(A) component" in the present disclosure), It is excellent in the easy release property of the mold layer and in the suppression of fine unevenness on the surface of the release layer. In the present disclosure, a polysiloxane chain means -silicon (Si)-oxygen (O)-[-silicon (Si)-oxygen (O)-] _L -silicon (Si)- (L is an integer of 1 or more. ) is a structure represented by

<(A1) Component>
As the (A1) component, those represented by the general formula (1) are exemplified.

（一般式（１）中、
χ_１～χ_２、χ_５～χ_６は、それぞれ独立に、エーテル結合及び／又はエステル結合を有していてもよく、並びに水酸基及び／又は（メタ）アクリロイルオキシ基を有していてもよい炭素数１以上２０以下の炭化水素基であり、
χ_３～χ_４は、それぞれ独立に、エーテル結合及び／又はエステル結合を有していてもよく、並びに水酸基及び／又は（メタ）アクリロイルオキシ基を有していてもよい炭素数１以上２０以下の炭化水素基であり、繰返し単位毎に同一であっても異なっていてもよく、
χ_１～χ_６のうち、少なくとも１個は水酸基を有しており、
χ_１～χ_６のうち、少なくとも１個は（メタ）アクリロイルオキシ基を有しており、
ψ_１～ψ_２は、それぞれ独立に、エーテル結合を有していてもよい炭素数１以上２０以下の直鎖状若しくは分岐状炭化水素基であり、
ｍは、１以上３００以下の整数であり。
ω_１～ω_４は水素原子である。） General formula (1):

(In general formula (1),
χ ₁ to χ ₂ and χ ₅ to χ ₆ may each independently have an ether bond and/or an ester bond, and may have a hydroxyl group and/or a (meth)acryloyloxy group. a hydrocarbon group having 1 to 20 carbon atoms,
χ ₃ to χ ₄ each independently optionally have an ether bond and/or an ester bond and optionally have a hydroxyl group and/or a (meth)acryloyloxy group and have 1 to 20 carbon atoms is a hydrocarbon group, which may be the same or different for each repeating unit,
at least one of χ ₁ to χ ₆ has a hydroxyl group,
At least one of χ ₁ to χ ₆ has a (meth)acryloyloxy group,
ψ ₁ to ψ ₂ are each independently a linear or branched hydrocarbon group having 1 to 20 carbon atoms which may have an ether bond,
m is an integer of 1 or more and 300 or less.
ω ₁ to ω ₄ are hydrogen atoms. )

The upper limit of the number of carbon atoms of χ ₁ to χ ₆ in general formula (1) is independently exemplified by 20, 18, 16, 14, 12, 10, 8, 6, 5, 4, 3, 2, etc. The lower limit is exemplified by 18, 16, 14, 12, 10, 8, 6, 5, 4, 3, 2, 1, and the like. In one embodiment, the number of carbon atoms in χ ₁ to χ ₆ in general formula (1) is preferably about 1 or more and 20 or less.

The “linear or branched hydrocarbon group having 1 to 20 carbon atoms which may have an ether bond” for ψ ₁ and ψ ₂ in the general formula (1) means It refers to a linear hydrocarbon group having 1 or more and 20 or less carbon atoms or a branched hydrocarbon group having 1 or more and 20 or less carbon atoms which may have an ether bond. The upper limit of the number of carbon atoms of ψ ¹ and ψ ² in general formula (1) is independently exemplified by 20, 18, 16, 14, 12, 10, 8, 6, 4, 2, etc., and the lower limit is 18. , 16, 14, 12, 10, 8, 6, 4, 2, 1, and the like. In one embodiment, the number of carbon atoms of ψ ₁ and ψ ₂ in general formula (1) is preferably approximately 1 or more and 20 or less. C _α H _2α-1 (α is an integer of 1 or more and 20 or less) as linear or branched hydrocarbon groups having 1 or more and 20 or less carbon atoms in ψ ₁ and ψ ₂ of general formula (1). A structure represented by is exemplified.

The upper limit of m in the general formula (1) is 300, 275, 250, 225, 200, 175, 150, 125, 100, 75, 50, 25, 10, 5, 3, etc., and the lower limit is 275, 250, 225, 200, 175, 150, 125, 100, 75, 50, 25, 10, 5, 3, 1, etc. are exemplified. In one embodiment, m in general formula (1) is an integer of 1 or more and 300 or less.

Specific examples of the component (A1) include the product name "KP-420" (manufactured by Shin-Etsu Chemical Co., Ltd.) and the product name "TEGO RAD 2100" (manufactured by Evonik Japan Co., Ltd.). TEGO RAD 2100 is a component having a (meth)acryloyloxy group in the side chain of polysiloxane from the descriptions of JP-A-2020-189948 and JP-A-2015-527424.

The upper limit of the number average molecular weight of component (A1) is 000, 10,000, 9,000, 8,000, 7,000, 6,000, 5,000, 4,000, 3,000, 2,000, 1,600, 1,400, 1,000, etc. are exemplified, and the lower limits are 19,000, 18,000, 17,000, 16,000, 15,000, 14,000, 13,000, 12,000, 11,000, 10,000, 9,000, 8,000, 7,000, 6,000, 5,000, 4,000, 3,000, 2,000, 1,600, 1,400, 1,200, 1,000, 500, etc. . In one embodiment, the number average molecular weight of component (A1) is preferably about 500 to 20,000. When the number average molecular weight of the component (A1) is 500 or more, the peelability is excellent. The higher the molecular weight of the component (A1), the easier the releasability tends to be. In the present disclosure, the number average molecular weight is a polystyrene-equivalent value obtained by gel permeation chromatography.

The upper limit of the functional group equivalent (g/mol) of component (A1) is 20,000, 19,000, 18,000, 17,000, 16,000, 15,000, 14,000, 13,000, 12 ,000, 11,000, 10,000, 9,000, 8,000, 7,000, 6,000, 5,000, 4,000, 3,000, 2,000, 1,600, 1,400 , 1,000, etc., and the lower limits are 19,000, 18,000, 17,000, 16,000, 15,000, 14,000, 13,000, 12,000, 11,000, 10,000 , 9,000, 8,000, 7,000, 6,000, 5,000, 4,000, 3,000, 2,000, 1,600, 1,400, 1,200, 1,000, 500 etc. are exemplified. In one embodiment, the functional group equivalent (g/mol) of component (A1) is preferably about 500 to 20,000. When the functional group equivalent (g/mol) of the component (A1) is 500 or more, the easy peelability is excellent. The higher the functional group equivalent (g/mol) of the component (A1), the easier the peelability tends to be. In addition, in this disclosure, the functional group equivalent is the molecular weight per functional group.

<(A2) component>
Component (A2) is a polysiloxane having a hydroxyl group (a1), a (meth)acrylate having a hydroxyl group (a2), a polyethylene glycol having a hydroxyl group at one end (a3), and a trifunctional or higher polyisocyanate (a4). is the reactant of Component (A2) is a urethane (meth)acrylate formed by the reaction of the hydroxyl groups of component (a1), the hydroxyl groups of component (a2), the hydroxyl groups of component (a3), and the isocyanate groups of component (a4).

Component (a1) is exemplified by hydroxyl-containing dimethylpolysiloxane and hydroxyl-containing diethylpolysiloxane. Examples of the position of the hydroxyl group of the component (a1) include both ends of the polysiloxane chain, one end of the polysiloxane chain, side chains of the polysiloxane chain, and the like.

The (a1) component may be a commercially available product. As the product, components containing —OH groups at both ends of polysiloxane (product names “KF-6000”, “KF-6001”, “KF-6002”, “KF-6003”, (manufactured by Shin-Etsu Chemical Co., Ltd. )), components containing —OH groups at one end of polysiloxane (product names “X-22-170BX”, “X-22-170DX”, “X-22-176DX”, “X-22-176F”, “ X-22-176GX-A” (manufactured by Shin-Etsu Chemical Co., Ltd.) (product names “Silaplane FM-0411”, “Silaplane FM-0421”, “Silaplane FM-0425”, “Silaplane FM- DA11", "Silaplane FM-DA21", and "Silaplane FM-DA26" (manufactured by JNC Corporation).

Component (a1) is preferably a dimethylpolysiloxane having a hydroxyl group, more preferably a dimethylpolysiloxane having one hydroxyl group, and even more preferably a dimethylpolysiloxane having one hydroxyl group at one end because of its good releasability. It is a dimethylpolysiloxane with

The upper limit of the number average molecular weight of component (a1) is 000, 10,000, 9,000, 8,000, 7,000, 6,000, 5,000, 4,000, 3,000, 2,000, 1,600, 1,400, 1,000, 800 etc. are exemplified, and the lower limits are 19,000, 18,000, 17,000, 16,000, 15,000, 14,000, 13,000, 12,000, 11,000, 10,000, 9,000, 000, 8,000, 7,000, 6,000, 5,000, 4,000, 3,000, 2,000, 1,600, 1,400, 1,200, 1,000, 800, 500, etc. are exemplified. In one embodiment, the number average molecular weight of component (a1) is preferably about 500 to 20,000, more preferably about 500 to 5,000, even more preferably about 500 to 3,000.

The upper limit of the functional group equivalent (g/mol) of component (a1) is 20,000, 19,000, 18,000, 17,000, 16,000, 15,000, 14,000, 13,000, 12 ,000, 11,000, 10,000, 9,000, 8,000, 7,000, 6,000, 5,000, 4,000, 3,000, 2,000, 1,600, 1,400 , 1,000, 800, etc., and the lower limits are 19,000, 18,000, 17,000, 16,000, 15,000, 14,000, 13,000, 12,000, 11,000, 10 ,000, 9,000, 8,000, 7,000, 6,000, 5,000, 4,000, 3,000, 2,000, 1,600, 1,400, 1,200, 1,000 , 800, 500, etc. are exemplified. In one embodiment, the functional group equivalent (g/mol) of component (a1) is preferably about 500 to 20,000, more preferably about 500 to 5,000, even more preferably about 500 to 3,000. .

The upper limit of the content (in terms of solid content) of component (a1) in the total amount of 100% by mass (in terms of solid content) of components (a1), (a2), (a3) and (a4) is 97, 95. , 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10, 5% by mass, etc., and the lower limits are 95, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10, 5, 1% by mass and the like are exemplified. In one embodiment, the content (in terms of solid content) of component (a1) in the total amount of 100% by mass (in terms of solid content) of components (a1), (a2), (a3) and (a4) is , about 1 to 50% by mass is preferable, about 1 to 40% by mass is more preferable, about 1 to 30% by mass is even more preferable, and about 1 to 20% by mass is particularly preferable. When the content is equal to or higher than the above lower limit, the light peelability is further improved. When the content is equal to or less than the above upper limit, suppression of surface unevenness, suppression of the amount of silicone migration, and emulsifiability are further improved.

(a2) components as 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 3-hydroxy-1-adamantyl (meth)acrylate, (meth)acrylic acid 2 -hydroxy-3-phenoxypropyl, glycerin di(meth)acrylate, 2-hydroxy-3-(meth)acryloyl-oxypropyl(meth)acrylate, 1-((meth)acryloyloxy)-3-(methacryloyloxy)- Examples include 2-propanol, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, and tripentaerythritol hepta(meth)acrylate.

The upper limit of the hydroxyl value (mgKOH/g) of component (a2) is 50, 40, 30, 20, 10, 5, etc. are exemplified, and the lower limits are 450, 400, 350, 300, 250, 200, 150, 140, 130, 120, 110, 100, 90, 80, 70, 60 , 50, 40, 30, 20, 10, 5, 1, and the like. In one embodiment, the hydroxyl value (mgKOH/g) of component (a2) is preferably 1-500, more preferably 10-500, and even more preferably 30-300.

The upper limit of the molecular weight of the component (a2) when calculated based on the atomic weight is 250, 200, 150, 100, 50, 25, etc. are exemplified, and the lower limits are 150, 100, 50, 25, 10, etc. are exemplified. In one embodiment, the molecular weight of component (a2) calculated on the basis of atomic weight is preferably 100-1,000, more preferably 200-600.

The upper limit of the content (in terms of solid content) of component (a2) in the total amount of 100% by mass (in terms of solid content) of components (a1), (a2), (a3) and (a4) is 97, 95. , 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10, 5% by mass, etc., and the lower limits are 95, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10, 5, 1% by mass and the like are exemplified. In one embodiment, the content (in terms of solid content) of component (a2) in the total amount of 100% by mass (in terms of solid content) of components (a1), (a2), (a3) and (a4) is , preferably about 1 to 70% by mass, more preferably about 5 to 65% by mass, even more preferably about 10 to 60% by mass, and particularly preferably about 15 to 50% by mass.

Component (a3) is a component having a hydroxyl group at one end of a polyethylene glycol chain (also referred to as “PEG chain” in the present disclosure). The component (a3) preferably has one hydroxyl group because it can suppress gelation due to the three-dimensional network structure caused by the reaction with the component (a4) and provides good light peelability. , and more preferably have one hydroxyl group at one end. Examples of component (a3) include polyethylene glycol monoalkyl ether, polyethylene glycol mono(meth)acrylate, polyethylene glycol monoallyl ether, and polyethylene glycol monoacylate.

Polyethylene glycol monoalkyl ethers include polyethylene glycol monomethyl ether, polyethylene glycol monoethyl ether, polyethylene glycol monopropyl ether, polyethylene glycol monobutyl ether, polyethylene glycol monopentyl ether, polyethylene glycol monohexyl ether, polyethylene glycol monoheptyl ether, polyethylene glycol monoalkyl ether. Octyl ether, polyethylene glycol lauryl ether, polyethylene glycol cetyl ether, polyethylene glycol stearyl ether, polyethylene glycol nonylphenyl ether, polyethylene glycol tridecyl ether, polyethylene glycol oleyl ether, polyethylene glycol octylphenyl ether, polyoxyethylene oleyl cetyl ether and the like are examples. be done.

Examples of polyethylene glycol mono(meth)acrylate include specific examples of polyethylene glycol mono(meth)acrylate described in Japanese Patent Publication No. 2021-017592.

Examples of polyethylene glycol monoallyl ether include specific examples of polyethylene glycol monoallyl ether described in Japanese Patent Publication No. 2021-017592.

Examples of polyethylene glycol monoacylate include specific examples of polyethylene glycol monoacylate described in Japanese Patent Publication No. 2021-017592.

The component (a3) is preferably represented by the following general formula (2) because it improves emulsifiability and satisfactorily exhibits various properties in the present disclosure.

General formula (2):
H—(OCH ₂ CH ₂ ) _n —OR
(In the formula, R represents an alkyl group having 1 to 4 carbon atoms, an allyl group, a (meth)acryloyl group, or an acyl group having 1 to 4 carbon atoms, and n represents an integer of 3 to 125. )

Component (a3) is particularly preferably polyethylene glycol monomethyl ether or polyethylene glycol mono(meth)acrylate.

The (a3) component may be a commercially available product. As the products, the product names "UNIOX M-400", "UNIOX M-550", "UNIOX M-1000", "UNIOX M-2000", "UNIOX M-2500", "UNIOX M -3000", "Uniox M-4000", "Blemmer PE-90", "Blemmer PE-200", "Blemmer PE-300", "Blemmer AE-90", "Blemmer AE-200", "Blemmer AE -400" (manufactured by NOF Corporation) and the like.

The upper limit of the hydroxyl value (mgKOH/g) of component (a3) is 50, 40, 30, 20, 10, 5, etc. are exemplified, and the lower limits are 450, 400, 350, 300, 250, 200, 150, 140, 130, 120, 110, 100, 90, 80, 70, 60 , 50, 40, 30, 20, 10, 5, 1, and the like. In one embodiment, the hydroxyl value (mgKOH/g) of component (a3) is preferably 10-500. In the present disclosure, the hydroxyl value is a value measured according to JIS K0070:1992.

The upper limit of the number average molecular weight of component (a3) is 800, 700, 600, 500, 400, 300, 200, etc. are exemplified, and the lower limits are 4,500, 4,000, 3,500, 3,000, 2,500, 2,000, 1,500, 1 , 000, 900, 800, 700, 600, 500, 400, 300, 200, 100 and the like. In one embodiment, the number average molecular weight of component (a3) is preferably 100 to 5,000, more preferably 200 to 3,000, still more preferably 300 to 2,000. When using (a3) having a number average molecular weight of 400 or less, it is particularly preferable to use a number average molecular weight of 800 or more in combination, because emulsifiability is improved and various properties of the present application are excellent. In the present disclosure, the number average molecular weight is a polystyrene equivalent value in gel permeation chromatography.

The upper limit of the content (in terms of solid content) of component (a3) in the total amount of 100% by mass (in terms of solid content) of components (a1), (a2), (a3) and (a4) is 97, 95. , 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10, 5% by mass, etc., and the lower limits are 95, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10, 5, 1% by mass and the like are exemplified. In one embodiment, the content (in terms of solid content) of component (a3) in the total amount of 100% by mass (in terms of solid content) of components (a1), (a2), (a3) and (a4) is , about 10 to 80% by mass, more preferably about 15 to 70% by mass, and even more preferably about 20 to 60% by mass.

Examples of component (a4) include triisocyanate and tetraisocyanate. Examples of triisocyanates include 4,4',4''-methylidyne tris(isocyanatobenzene), lysine triisocyanate, and various isocyanate oligomers (eg, isocyanurates, adducts, biurets, etc.). Examples of tetraisocyanates include polymers of various isocyanates (eg, isocyanurates, adducts, biurets, etc.). Examples of various isocyanates include linear aliphatic polyfunctional isocyanates, branched aliphatic polyfunctional isocyanates, alicyclic polyfunctional isocyanates, and aromatic polyfunctional isocyanates. Examples of linear aliphatic polyfunctional isocyanates include trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, octamethylene diisocyanate, and decamethylene diisocyanate. Examples of branched aliphatic polyfunctional isocyanates include methyl diisocyanatohexanoate and trimethylhexamethylene diisocyanate. Examples of alicyclic polyfunctional isocyanates include dicyclohexylmethane diisocyanate, isophorone diisocyanate, bis(isocyanatomethyl)cyclohexane, cyclohexanediylbis(methylene)diisocyanate, methylcyclohexanediyl diisocyanate, norbornenemethane diisocyanate, and the like. Examples of aromatic polyfunctional isocyanates include toluenediisocyanate, xylene diisocyanate, diisocyanatonaphthalene, and the like. By using a trifunctional or higher isocyanate as component (a4), the ratio of components having structures derived from components (a1), (a2), and (a3) in the same molecule increases, and component (a2) It is preferable because it can suppress the formation of components that do not have a derived structure, and exhibits good silicone transferability.

The upper limit of the number average molecular weight of component (a4) is 800, 700, 600, 500, 400, 300, 200, etc. are exemplified, and the lower limits are 4,500, 4,000, 3,500, 3,000, 2,500, 2,000, 1,500, 1 , 000, 900, 800, 700, 600, 500, 400, 300, 200, 100 and the like. In one embodiment, the number average molecular weight of component (a4) is preferably 400-5,000.

The upper limit of the content (in terms of solid content) of component (a4) in the total amount of 100% by mass (in terms of solid content) of components (a1), (a2), (a3) and (a4) is 97, 95. , 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10, 5% by mass, etc., and the lower limits are 95, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10, 5, 1% by mass and the like are exemplified. In one embodiment, the content (in terms of solid content) of component (a4) in the total amount of 100% by mass (in terms of solid content) of components (a1), (a2), (a3) and (a4) is , about 5 to 60% by mass, more preferably about 10 to 50% by mass, and even more preferably about 15 to 40% by mass.

The upper limit of the number of (meth)acryloyl groups in component (a2) is exemplified by 20, 18, 16, 14, 12, 10, 8, 6, 5, 4, 3, 2, etc., and the lower limit is 18, 16, 14, 12, 10, 8, 6, 5, 4, 3, 2, 1, etc. are exemplified. In one embodiment, the number of (meth)acryloyl groups in component (a2) is preferably about 1-20. The upper limit of the number of hydroxyl groups of the component (a1), the hydroxyl groups of the component (a2), the hydroxyl groups of the component (a3), and the isocyanate groups of the component (a4) are exemplified by 5, 4, 3, 2, etc., and the lower limit is 4, 3, 2, 1, etc. are exemplified. In one embodiment, the number of hydroxyl groups in component (a1), hydroxyl groups in component (a2), hydroxyl groups in component (a3), and isocyanate groups in component (a4) is preferably about 1 to 5.

The molar ratio of the hydroxyl groups of component (a1), the hydroxyl groups of component (a2), the hydroxyl groups of component (a3), and the isocyanate groups of component (a4) (hydroxyl groups of component (a1)/hydroxyl groups of component (a2)/component (a3) The hydroxyl group of / (a4) component isocyanate group) is
0.01 or more and 1.0 or less/1.0 or more/0.5 or more and 2.0 or less/2.5 or more and 6.0 or less,
0.01 or more and 1.0 or less/1.0 or more and 6.0 or less/0.5 or more and 2.0 or less/2.5 or more and 6.0 or less,
0.05 or more and 0.5 or less/1.0 or more and 4.0 or less/0.5 or more and 1.5 or less/2.5 or more and 5.0 or less,
0.08 or more and 0.3 or less/1.5 or more and 3.5 or less/0.7 or more and 1.3 or less/2.5 or more and 4.0 or less,
Examples include 0.09 or more and 0.2 or less/2.0 or more and 3.0 or less/0.8 or more and 1.3 or less/2.5 or more and 3.5 or less.

Components other than the (a1) component, the (a2) component, the (a3) component and the (a4) component may be included as components constituting the (A2) component. Examples of the other component include compounds having at least one functional group capable of reacting with an isocyanate group or a hydroxyl group in the molecule. A hydroxyl group, an amino group, etc. are illustrated as the said isocyanate group and a reactive functional group. An isocyanate group, a carboxyl group, etc. are illustrated as the said hydroxyl group and a reactive functional group.

The method for producing component (A2) using component (a1), component (a2), component (a3) and component (a4) comprises: component (a1), component (a2), component (a3) and component (a4) is not particularly limited as long as it is a method of reacting. Specifically, for example, the components (a1), (a3) and (a4) are combined with a catalyst (organic tin (tin octylate, octyltin dilaurate, etc.), organic zirconium (zirconium tetraacetylacetonate, etc.), etc. ) in the presence of a suitable reaction temperature (e.g. 60 ~ 90 ° C., etc.), (a2) component is added, similarly in the presence of a catalyst, an appropriate reaction temperature (e.g. 60 ~ 90 ° C., etc.) ) and the like. The order of addition of components (a1), (a2), (a3), and (a4) is not particularly limited. Component, (a2), (a3), and (a4) are reacted at a feed ratio such that the NCO group is at least an equimolar ratio to the OH group, and then newly or additionally remaining By adding the component (a2) in an amount such that the ratio of the OH groups to the NCO groups is at least equimolar, it is possible to suppress the formation of components that do not contain (meth)acryloyl groups, and the silicone migration property is improved. Therefore, it is preferable. When reacted by this method, the component (A2) is a mixture of the reactants of the components (a1), (a2), (a3) and (a4), and the excess amount of the component (a2). Become. Organic diluents can also be included at appropriate points in these methods.

The substances exemplified as component (A) and those known as component (A) can be used alone or in combination of two or more.

The upper limit of the content (in terms of solid content) of component (a1) in the total amount of 100% by mass (in terms of solid content) of components (A), (B), and (C) is 95, 90, 85, 80. , 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10, 5, 1.5, 1, 0.5, 0.1% by mass, etc. , lower limits of 0.1, 0.05% by mass and the like are exemplified. In one embodiment, the content (in terms of solid content) of component (a1) in the total amount of 100% by mass (in terms of solid content) of components (A), (B), and (C) is 0.05. About 10% by mass is preferable, about 0.1 to 5% by mass is more preferable, and about 0.1 to 1.5% by mass is even more preferable. The content of component (a1) (calculated as solid content) in the total amount of 100% by mass (calculated as solid content) of components (A), (B), and (C) remained unreacted in the system. The sum of the contents of component (a1) and component (a1) reacted with other components and incorporated into component (A) was divided by the total amount of component (A), component (B), and component (C). means value.

The upper limit of the content (in terms of solid content) of component (A) in the total amount of 100% by mass (in terms of solid content) of components (A), (B), and (C) is 98, 95, 90, 85. , 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10, 5, 4, 3, 2% by mass, etc., and the lower limit is 95, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10, 5, 4, 3, 2, 1% by mass, etc. . In one embodiment, the content (in terms of solid content) of component (A) in the total amount of 100% by mass (in terms of solid content) of component (A), component (B), and component (C) is 1 to 50. About mass % is preferable, about 2 to 40 mass % is more preferable, and about 3 to 30 mass % is even more preferable.

<(B) Component>
The component (B) is a urethane (meth)acrylate that is a reaction product of components containing a hydroxyl group-containing (meth)acrylate (b1), a hydroxyl group-containing polyethylene glycol (b2), and a polyisocyanate (b3). Containing a polyalkylene glycol chain (especially a PEG chain) improves emulsifiability and can exhibit various properties in the present disclosure.

<(b1) component>
The (b1) component is a (meth)acrylate having a hydroxyl group. Examples of the type and various parameters (molecular weight, etc.) of the (b1) component include (meth)acrylates having a hydroxyl group and various parameters (molecular weight, etc.) exemplified in the description of the (a2) component.

The upper limit of the content (in terms of solid content) of component (b1) in the total amount of 100% by mass (in terms of solid content) of components (b1), (b2), and (b3) is 98, 95, 90, 85. , 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10, 5% by mass, etc., and the lower limits are 95, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10, 5, 1% by mass and the like are exemplified. In one embodiment, the content (in terms of solid content) of component (b1) in the total amount of 100% by mass (in terms of solid content) of components (b1), (b2), and (b3) is 1 to 98. About % by mass is preferable.

<(b2) component>
Component (b2) is polyethylene glycol having a hydroxyl group. Examples of component (b2) include polyethylene glycols, polyethylene glycol monoalkyl ethers, polyethylene glycol mono(meth)acrylates, polyethylene glycol monoallyl ethers, and polyethylene glycol monoacylates.

Polyethylene glycols include polyethylene glycol, polyethylene glycol polypropylene glycol polyethylene glycol (block copolymer), polypropylene glycol polyethylene glycol polypropylene glycol (block copolymer), polyethylene glycol polypropylene glycol (random copolymer), polyoxytetramethylene glycol polyethylene glycol polyoxytetramethylene Glycol (block copolymer), polyethylene glycol polyoxytetramethylene glycol polyethylene glycol (block copolymer), polyethylene glycol polyoxytetramethylene glycol (random copolymer) and the like are exemplified.

Examples of polyethylene glycol monoalkyl ethers include polyethylene glycol monoalkyl ethers described in component (a3).

Examples of polyethylene glycol mono(meth)acrylates include polyethylene glycol mono(meth)acrylate, polyethylene glycol polypropylene glycol mono(meth)acrylate, poly(ethylene glycol tetramethylene glycol) mono(meth)acrylate and the like.

Examples of polyethylene glycol monoallyl ethers include polyethylene glycol monoallyl ether, polyethylene glycol polypropylene glycol monoallyl ether, and the like.

Examples of polyethylene glycol monoacylates include polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol monooleate and the like.

Other preferred examples of component (b2) and various parameters (hydroxyl value, etc.) are the same as those described in (a3).

The upper limit of the content (in terms of solid content) of component (b2) in the total amount of 100% by mass (in terms of solid content) of components (b1), (b2), and (b3) is 98, 95, 90, 85. , 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10, 5% by mass, etc., and the lower limits are 95, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10, 5, 1% by mass and the like are exemplified. In one embodiment, the content (in terms of solid content) of component (b2) in the total amount of 100% by mass (in terms of solid content) of components (b1), (b2), and (b3) is 1 to 98. About % by mass is preferable.

<(b3) Component>
The (b3) component is a polyisocyanate. Examples of the type and various parameters (number average molecular weight, etc.) of the (b3) component include the triisocyanate, tetraisocyanate, and various parameters (number average molecular weight, etc.) exemplified in the description of the component (a4). Other types of component (b3) include various known diisocyanates.

The upper limit of the content (in terms of solid content) of component (b3) in the total amount of 100% by mass (in terms of solid content) of components (b1), (b2), and (b3) is 98, 95, 90, 85. , 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10, 5% by mass, etc., and the lower limits are 95, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10, 5, 1% by mass and the like are exemplified. In one embodiment, the content (in terms of solid content) of component (b3) in the total amount of 100% by mass (in terms of solid content) of components (b1), (b2), and (b3) is 1 to 98. About % by mass is preferable.

The substances exemplified as component (B) and those known as component (B) can be used alone or in combination of two or more.

The molar ratio of the hydroxyl groups of component (b1), the hydroxyl groups of component (b2), and the isocyanate groups of component (b3) ([hydroxyl groups of component (b1)/hydroxyl groups of component (b2)/isocyanate groups of component (b3)]) teeth,
0.5 or more/0.3 or more and 2.5 or less/2.5 or more and 6.0 or less 0.5 or more and 6.0 or less/0.3 or more and 2.5 or less/2.5 or more and 6.0 or less1. 0-5.0/0.3-2.0/2.5-5.0/2.0-4.0/0.3-1.5/2.5-4.0 Examples include 2.5 or more and 3.5 or less/0.5 or more and 1.0 or less/2.5 or more and 3.5 or less.

The upper limit of the content ratio (mass ratio, solid content conversion, [(A) component/(B) component]) of component (A) and component (B) is 99/1, 95/5, 90/10, 85/15, 80/20, 75/25, 70/30, 65/35, 60/40, 55/45, 50/50, 45/55, 40/60, 35/65, 30/70, 25/ 75, 20/80, 15/85, 10/90, 5/95, etc. are exemplified, and the lower limits are 95/5, 90/10, 85/15, 80/20, 75/25, 70/30, 65 /35, 60/40, 55/45, 50/50, 45/55, 40/60, 35/65, 30/70, 25/75, 20/80, 15/85, 10/90, 5/95 , 1/99, and the like. In one embodiment, the content ratio (mass ratio, in terms of solid content, [(A) component/(B) component]) of component (A) and component (B) is about 1/99 to 99/1. is preferred.

The upper limit of the content (in terms of solid content) of component (B) in the total amount of 100% by mass (in terms of solid content) of components (A), (B), and (C) is 98, 95, 90, 85. , 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10, 5% by mass, etc., and the lower limits are 95, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10, 5, 1% by mass and the like are exemplified. In one embodiment, the content (as solid content) of component (B) in the total amount of 100% by mass (as solid content) of component (A), component (B), and component (C) is 1 to 98. About % by mass is preferable.

The method for producing component (B) is not particularly limited as long as it is a method of reacting components (b1), (b2) and (b3), and various known production methods are exemplified. Specifically, for example, component (b2) and component (b3) are reacted in the presence of a catalyst at an appropriate reaction temperature (eg, 60 to 90° C.), then component (b1) is added, and the like. A method of reacting components (b1), (b2) and (b3) in the presence of a catalyst at an appropriate reaction temperature (eg, 60 to 90 ° C.) in the presence of a catalyst, at an appropriate reaction temperature (eg 60 to 90°C, etc.), then adding an additional component (b1), and reacting at an appropriate reaction temperature (eg, 60 to 90°C, etc.) in the presence of a catalyst.

<(C) Component>
One or more (C) selected from polyfunctional (meth)acrylate (c1) and polyfunctional (meth)acrylamide (c2) in the aqueous emulsion composition of the present disclosure (also referred to as "(C) component" in the present disclosure) ), the scratch resistance is excellent. The (c1) component is a polyfunctional (meth)acrylate other than the (A) component and the (B) component.

Examples of component (c1) include di(meth)acrylate, tri(meth)acrylate, tetra(meth)acrylate, penta(meth)acrylate, hexa(meth)acrylate, and poly(meth)acrylate. Di(meth)acrylates such as ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, erythritol di(meth)acrylate, pentaerythritol di(meth)acrylate, dipentaerythritol di( meth)acrylate and the like are exemplified. Tri(meth)acrylates include trimethylolpropane tri(meth)acrylate, ethylene oxide-modified trimethylolpropane tri(meth)acrylate, propylene oxide-modified trimethylolpropane tri(meth)acrylate, propylene oxide-modified glycerol (meth)acrylate, penta Erythritol tri(meth)acrylate and the like are exemplified. Examples of tetra(meth)acrylates include pentaerythritol tetra(meth)acrylate, ethylene oxide-modified pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, and ditrimethylolpropane tetra(meth)acrylate. Examples of penta(meth)acrylate include dipentaerythritol penta(meth)acrylate and the like. Examples of hexa(meth)acrylate include dipentaerythritol hexa(meth)acrylate, ethylene oxide-modified dipentaerythritol hexa(meth)acrylate, and the like. Examples of poly(meth)acrylates include pentaerythritol poly(meth)acrylate, dipentaerythritol poly(meth)acrylate, tripentaerythritol poly(meth)acrylate, and glycerin poly(meth)acrylate. In the present disclosure, poly(meth)acrylate refers to a mixture of substances having multiple types of (meth)acryloyl groups.

Other (c1) components include urethane (meth)acrylate, polyester (meth)acrylate, epoxy (meth)acrylate and the like.

Various known methods are exemplified as methods for synthesizing urethane (meth)acrylate. As various known methods for synthesizing urethane (meth)acrylates, (1) a prepolymer having an isocyanate group obtained by urethanization reaction of a polyol and a polyisocyanate is further subjected to a urethanization reaction with a hydroxyl group-containing (meth)acrylate;
(2) A method of reacting a prepolymer having a hydroxyl group obtained by urethanizing a polyol and a polyisocyanate with an isocyanate group-containing (meth)acrylate,
(3) a method of reacting a polyisocyanate with a hydroxyl group-containing (meth)acrylate;
(4) A method of reacting a polyol with an isocyanate group-containing (meth)acrylate is exemplified.
In the method for synthesizing urethane (meth)acrylate, various known catalysts (such as dibutyltin dilaurate) can be appropriately used as necessary.
In the synthesis method of urethane (meth)acrylate, it is possible to obtain by reacting each component under the temperature and pressure at the time of urethanization reaction.

Polyols such as polyether polyol, polyester polyol, polycarbonate polyol, acrylic polyol, polyolefin polyol, neopentyl glycol, 3-methyl-1,5-pentanediol, ethylene glycol, propylene glycol, 1,4-butanediol, 1,6 -hexanediol, trimethylolpropane, pentaerythritol, tricyclodecanedimethylol, bis-[hydroxymethyl]-cyclohexane and the like.

Examples of polyisocyanates include polyisocyanates containing chain hydrocarbon groups, polyisocyanates containing alicyclic hydrocarbon groups, and polyisocyanates containing aromatic hydrocarbon groups. Examples of polyisocyanates containing chain hydrocarbon groups include hexamethylene diisocyanate. Examples of polyisocyanates containing alicyclic hydrocarbon groups include isophorone diisocyanate and dicyclohexylmethane diisocyanate. Examples of polyisocyanates containing aromatic hydrocarbon groups include tolylene diisocyanate, xylene diisocyanate, diphenylmethane-4,4'-diisocyanate, 3-methyldiphenylmethane diisocyanate, and the like. Examples of other polyisocyanates include 1,5-naphthalenediisocyanate, adducts of the above-exemplified polyisocyanates and various known polyisocyanates, polymers of these isocyanates, and the like. Examples of such polyisocyanates include biurets, nurates, adducts, allophanates and the like. Examples of polyisocyanate biuret include product names "Duranate 24A-100", "Biuret 22A-75P", and "Biuret 21S-75E" (all manufactured by Asahi Kasei Corporation). Examples of polyisocyanate nurate include product names "Coronate HK" and "Coronate HXR" (both manufactured by Tosoh Corporation). Examples of polyisocyanate adducts include the product name "Coronate HL" (manufactured by Tosoh Corporation). Examples of allophanates of polyisocyanates include the product name "Coronate 2770" (manufactured by Tosoh Corporation). Further, the polyisocyanate of the present disclosure may have an average number of isocyanate groups of about 3 or more and 10 or less. In addition, the average number of isocyanate groups can be calculated by the following formula. Average number of isocyanate groups = (number average molecular weight (Mn) x isocyanate group concentration (%))/(42.02 x 100). The isocyanate group concentration (%) in the formula is a value measured by the method described in JIS K 1603-1:2007.

As hydroxyl group-containing (meth)acrylates, hydroxyl group-containing (meth)acrylates containing a chain hydrocarbon group, hydroxyl group-containing (meth)acrylates containing an alicyclic hydrocarbon group, and hydroxyl group-containing (meth)acrylates containing an aromatic hydrocarbon group etc. are exemplified. Hydroxyl group-containing (meth)acrylates containing a chain hydrocarbon group include 1-hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 2-hydroxybutyl (meth)acrylate. , 4-hydroxybutyl (meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate and the like. Examples of hydroxyl group-containing (meth)acrylates containing alicyclic hydrocarbon groups include 4-(hydroxymethyl)cyclohexylmethyl (meth)acrylate and the like. Hydroxyphenyl (meth)acrylate etc. are illustrated as a hydroxyl-containing (meth)acrylate containing an aromatic-hydrocarbon group.

As isocyanate group-containing (meth)acrylates, 2-isocyanatoethyl (meth)acrylate, 2-(2-(meth)acryloyloxyethyloxy)ethyl isocyanate, 1,1-(bis(meth)acryloyloxymethyl)ethyl) Isocyanate and the like are exemplified.

As the (c2) component, bifunctional (meth)acrylamide (N,N'-diacryloyl-4,7,10-trioxa-1,13-tridecanediamine, etc.), trifunctional (meth)acrylamide (N, N′,N″-triacryloyldiethylenetriamine, 1,3,5-triacryloylhexahydro-1,3,5-triazine, etc.), tetrafunctional (meth)acrylamides (N,N′-{[(2- acrylamide-2-[(3-acrylamidopropoxy)methyl]propane-1,3-diyl)bis(oxy)]bis(propane-1,3-diyl)}diacrylamide, N,N',N'',N '''-tetraacryloyltriethylenetetramine, etc.).

(C) A component may be a commercial item. Such products include pentaerythritol poly(meth)acrylate (product names “Aronix M-933”, “Aronix M-934”, “Aronix M-306”, “Aronix M-305”, manufactured by Toagosei Co., Ltd.), glycerin Poly (meth) acrylate (product name "Aronix M-920", "Aronix M-930" Toagosei Co., Ltd.), ditrimethylolpropane tetra (meth) acrylate (product name "Aronix M-408", Toagosei ( Co.), N,N'-{[(2-acrylamido-2-[(3-acrylamidopropoxy)methyl]propane-1,3-diyl)bis(oxy)]bis(propane-1,3-diyl )} diacrylamide (product name “FAM-401”, manufactured by FUJIFILM Corporation) and the like.

The substances exemplified as component (C) and those known as component (C) can be used alone or in combination of two or more.

The upper limit of the hydroxyl value (mgKOH/g) of the component (c1) is exemplified by 800, 700, 600, 500, 450, 400, 350, 300, 250, 200, 150, 100, 50, 25, 10, etc. Examples of lower limits include 700, 600, 500, 450, 400, 350, 300, 250, 200, 150, 100, 50, 25, 10, 0, and the like. The higher the hydroxyl value (mgKOH/g) of the component (c1), the better the value of Sq, which indicates the ability to suppress surface unevenness of the cured product of the water-based emulsion composition. In addition, when the curing method of the water-based emulsion composition is heat curing, and a certain temperature and time can be applied, even if the component (c1) has a low hydroxyl value, the cured product of the water-based emulsion composition can suppress unevenness. The numerical value of Sq representing is good. Component (c1) preferably contains component (c1) with a high hydroxyl value, since the value of Sq, which indicates the ability to suppress surface unevenness of the cured product of the aqueous emulsion composition, is good regardless of the curing method. .

The upper limit of the number of (meth)acryloyl groups in component (C) is 30, 25, 20, 15, 10, 9, 8, 7, 6, 5, 4, 3, etc., and the lower limit is 25, 20, 15, 10, 9, 8, 7, 6, 5, 4, 3, 2, etc. are exemplified. In one embodiment, the number of (meth)acryloyl groups in component (C) is preferably 2 to 30.

The upper limit of the content ratio of component (A) to component (C) (mass ratio, in terms of solid content, [(A) component/(C) component]) is 99/1, 95/5, 90/10, 85/15, 80/20, 75/25, 70/30, 65/35, 60/40, 55/45, 50/50, 45/55, 40/60, 35/65, 30/70, 25/ 75, 20/80, 15/85, 10/90, 5/95, etc. are exemplified, and the lower limits are 95/5, 90/10, 85/15, 80/20, 75/25, 70/30, 65 /35, 60/40, 55/45, 50/50, 45/55, 40/60, 35/65, 30/70, 25/75, 20/80, 15/85, 10/90, 5/95 , 1/99, and the like. In one embodiment, the content ratio (mass ratio, solid content conversion, [(A) component/(C) component]) of component (A) and component (C) is about 1/99 to 60/40. is preferable, about 1/99 to 50/50 is more preferable, and about 5/95 to 45/55 is even more preferable.

The upper limit of the content ratio of component (B) to component (C) (mass ratio, in terms of solid content, [(B) component/(C) component]) is 99/1, 95/5, 90/10, 85/15, 80/20, 75/25, 70/30, 65/35, 60/40, 55/45, 50/50, 45/55, 40/60, 35/65, 30/70, 25/ 75, 20/80, 15/85, 10/90, 5/95, etc. are exemplified, and the lower limits are 95/5, 90/10, 85/15, 80/20, 75/25, 70/30, 65 /35, 60/40, 55/45, 50/50, 45/55, 40/60, 35/65, 30/70, 25/75, 20/80, 15/85, 10/90, 5/95 , 1/99, and the like. In one embodiment, the content ratio of component (B) to component (C) (mass ratio, in terms of solid content, [(B) component/(C) component]) is about 5/95 to 99/1. is preferred, about 10/90 to 99/1 is more preferred, and about 20/80 to 99/1 is even more preferred.

The upper limit of the content (in terms of solid content) of component (C) in the total amount of 100% by mass (in terms of solid content) of components (A), (B), and (C) is 98, 95, 90, 85. , 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10, 5% by mass, etc., and the lower limits are 95, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10, 5, 1% by mass and the like are exemplified. In one embodiment, the content (in terms of solid content) of component (C) in the total amount of 100% by mass (in terms of solid content) of components (A), (B), and (C) is 1 to 80. About mass % is preferable, about 1 to 70 mass % is more preferable, about 1 to 60 mass % is even more preferable, and about 1 to 55 mass % is most preferable.

The upper limit of the sum of the contents (in terms of solid content) of component (a2) and component (C) in the total amount of 100% by mass (in terms of solid content) of components (A), (B), and (C) is 98, 95, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10, 5 mass%, etc., and the lower limit is 95 , 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10, 5, 1% by mass, and the like. In one embodiment, the content of component (a2) and component (C) in the total amount of 100% by mass (in terms of solid content) of component (A), component (B), and component (C) (in terms of solid content) is preferably about 1 to 80% by mass, more preferably about 1 to 75% by mass, and even more preferably about 1 to 70% by mass. By setting the compounding ratio to satisfy the above, it is possible to obtain a cured film exhibiting good solvent resistance, easy release property, and silicone migration property. Further, the molar ratio of the hydroxyl groups of the preferred component (a1), the hydroxyl groups of the component (a2), the hydroxyl groups of the component (a3), and the isocyanate groups of the component (a4) (hydroxyl groups of the component (a1)/hydroxyl groups of the component (a2) / hydroxyl group of component (a3) / isocyanate group of component (a4)), even if component (a2) is added in an excessive amount beyond the range of (A) component, (B) component, and (C) component By setting the sum of the contents (in terms of solid content) of component (a2) and component (C) in the total amount of 100% by mass (in terms of solid content) within the above range, the cured film has good solvent resistance and easy peeling. and silicone transferability can be maintained.

<(D) Component>
The aqueous emulsion composition of the present disclosure may contain a photopolymerization initiator (D) (also referred to as “(D) component” in the present disclosure).

Examples of component (D) include radical photopolymerization initiators and anionic photopolymerization initiators. Examples of radical photopolymerization initiators include alkylphenone type photopolymerization initiators, acylphosphine oxide type photopolymerization initiators, hydrogen abstraction type photopolymerization initiators, oxime ester type photopolymerization initiators, and the like. As alkylphenone-type photopolymerization initiators, benzyl dimethyl ketal such as 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy- 2-methyl-1-propan-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propan-1-one , 1-hydroxy-cyclohexyl-phenylketone and other α-hydroxyalkylphenones, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino -1-(4-morpholinophenyl)-1-butanone, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone Examples include α-aminoalkylphenones such as Examples of acylphosphine oxide type photopolymerization initiators include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide. Examples of the hydrogen abstraction type photopolymerization initiator include phenylglyoxylic acid methyl ester and the like. As oxime ester type photopolymerization initiators, 1,2-octanedione, 1-[4-(phenylthio)-, 2-(O-benzoyloxime)], ethanone, 1-[9-ethyl-6-(2- Methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime) and the like are exemplified. Examples of anionic photopolymerization initiators include cobalt amine complexes, o-nitrobenzyl alcohol carbamate esters, oxime esters, and the like.

The substances exemplified as component (D) and those known as component (D) can be used alone or in combination of two or more.

Component (D) is particularly excellent in curability, so it is preferably a radical photopolymerization initiator, more preferably an alkylphenone photopolymerization initiator, and even more preferably α-hydroxyalkylphenone and/or α -aminoalkylphenone, particularly preferably 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-{4- [4-(2-Hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propan-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone and 2-methyl-1-(4 -methylthiophenyl)-2-morpholinopropan-1-one.

A commercially available product may be used as the component (D). The product is not particularly limited, but 2,2-dimethoxy-1,2-diphenylethan-1-one (product name “Omnirad 651”, manufactured by IGM Resins), 1-[4-(2-hydroxyethoxy) -Phenyl]-2-hydroxy-2-methyl-1-propan-1-one (product name "Omnirad 2959", manufactured by IGM Resins), 2-hydroxy-1-{4-[4-(2-hydroxy- 2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propan-1-one (product name “Omnirad 127”, manufactured by IGM Resins), 1-hydroxy-cyclohexyl-phenylketone (product name “Omnirad 184 ”, manufactured by IGM Resins), 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one (product name “Omnirad 907”, manufactured by IGM Resins), 2-benzyl-2- Dimethylamino-1-(4-morpholinophenyl)-1-butanone (product name "Omnirad 369E", manufactured by IGM Resins), 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1 -[4-(4-morpholinyl)phenyl]-1-butanone (product name “Omnirad 379EG”, manufactured by IGM Resins), 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (product name “Omnirad TPO H ”, manufactured by IGM Resins), bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (product name “Omnirad 819”, manufactured by IGM Resins), phenylglyoxylic acid methyl ester (product name “Omnirad MBF", manufactured by IGM Resins), 1,2-octanedione, 1-[4-(phenylthio)-, 2-(O-benzoyloxime)] (product name "IRGACURE OXE 01", manufactured by BASF Japan Ltd. ), ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime) (product name “IRGACURE OXE 02”, BASF Japan ( Co., Ltd.) and the like are exemplified.

The upper limit of the content ratio of component (A) to component (D) (mass ratio, in terms of solid content, [(A) component/(D) component]) is 99/1, 95/5, 90/10, 85/15, 80/20, 75/25, 70/30, 65/35, 60/40, 55/45, 50/50, 45/55, 40/60, 35/65, 30/70, 25/ 75, 20/80, etc., and the lower limits are 95/5, 90/10, 85/15, 80/20, 75/25, 70/30, 65/35, 60/40, 55/45, 50 /50, 45/55, 40/60, 35/65, 30/70, 25/75, 20/80, 15/85 and the like are exemplified. In one embodiment, the content ratio (mass ratio, in terms of solid content, [(A) component/(D) component]) of component (A) and component (D) is about 15/85 to 99/1. is preferred, about 15/85 to 95/5 is more preferred, and about 15/85 to 90/10 is even more preferred.

The upper limit of the content ratio of component (B) to component (D) (mass ratio, converted to solid content, [(B) component/(D) component]) is 99/1, 95/5, 90/10, 85/15, 80/20, 75/25, 70/30, 65/35, 60/40, 55/45, 50/50, 45/55, 40/60, 35/65, 30/70, 25/ 75, 20/80, 15/85, 10/90, 5/95, etc. are exemplified, and the lower limits are 95/5, 90/10, 85/15, 80/20, 75/25, 70/30, 65 /35, 60/40, 55/45, 50/50, 45/55, 40/60, 35/65, 30/70, 25/75, 20/80, 15/85, 10/90, 5/95 , 1/99, and the like. In one embodiment, the content ratio of component (B) to component (D) (mass ratio, in terms of solid content, [(B) component/(D) component]) is about 40/60 to 99/1. is preferred, about 45/55 to 95/5 is more preferred, and about 50/50 to 95/5 is even more preferred.

The upper limit of the content ratio of component (C) to component (D) (mass ratio, in terms of solid content, [(C) component/(D) component]) is 95/5, 90/10, 85/15, 80/20, 75/25, 70/30, 65/35, 60/40, 55/45, 50/50, 45/55, 40/60, 35/65, 30/70, 25/75, 20/ 80, 15/85, 10/90, etc. are exemplified, and the lower limits are 90/10, 85/15, 80/20, 75/25, 70/30, 65/35, 60/40, 55/45, 50 /50, 45/55, 40/60, 35/65, 30/70, 25/75, 20/80, 15/85, 10/90, 5/95 and the like. In one embodiment, the content ratio (mass ratio, in terms of solid content, [(C) component/(D) component]) of component (C) and component (D) is about 5/95 to 95/5. is preferred, and about 10/90 to 95/5 is more preferred.

The upper limits of the content (in terms of solid content) of component (D) with respect to the total amount of 100% by mass (in terms of solid content) of components (A), (B), and (C) are 50, 45, 40, 35, 30, 25, 20, 15, 10, 5, 3, 2, 1, 0.5% by mass, etc. are exemplified, and the lower limits are 45, 40, 35, 30, 25, 20, 15, 10, 5, 3 , 2, 1, 0.5, 0% by mass, and the like. In one embodiment, the content of component (D) relative to the total amount of component (A), component (B), and component (C) of 100% by mass (in terms of solid content) (in terms of solid content) is 2 to 25 mass. % is preferable.

<(E) component>
The aqueous emulsion composition of the present disclosure may contain an organic diluent (E) (also referred to as “component (E)” in the present disclosure). Examples of component (E) include monofunctional monomers and organic solvents.

As monofunctional monomers, a (meth)acrylate having an alkyl group having 1 to 30 carbon atoms, a (meth)acrylate having an alicyclic structure having 3 to 30 carbon atoms, and an aromatic structure having 6 to 30 carbon atoms. a (meth)acrylate having a heterocyclic structure having 3 to 30 carbon atoms, a vinyl compound having 2 to 30 carbon atoms, and the like. Examples of (meth)acrylates having an alkyl group having 1 to 30 carbon atoms include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, and n-butyl (meth)acrylate. , isobutyl (meth)acrylate, t-butyl (meth)acrylate, n-pentyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-hexyl acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, n-dodecyl acrylate, lauryl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, isostearyl ( Examples include meth)acrylate and behenyl (meth)acrylate. Examples of (meth)acrylates having an alicyclic structure having 3 to 30 carbon atoms include isobornyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyloxyethyl (meth) Examples include acrylate, adamantane (meth)acrylate, cyclohexyl acrylate and the like. Examples of (meth)acrylates having an aromatic structure with 6 to 30 carbon atoms include phenoxyethyl (meth)acrylate and benzyl (meth)acrylate. Examples of (meth)acrylates having a heterocyclic structure with 3 to 30 carbon atoms include tetrahydrofurfuryl (meth)acrylate. Examples of vinyl compounds having 2 to 30 carbon atoms include styrene, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, N-vinylformamide, N-vinylpyrrolidone, N-vinylcaprolactam and the like.

Examples of organic solvents include ketone solvents, aromatic solvents, alcohol solvents, glycol solvents, glycol ether solvents, ester solvents, petroleum solvents, haloalkane solvents, amide solvents and the like. Examples of ketone solvents include methyl ethyl ketone, acetylacetone, methyl isobutyl ketone, cyclopentanone, cyclohexanone and the like. Examples of aromatic solvents include toluene and xylene. Examples of alcohol solvents include methanol, ethanol, n-propanol, isopropanol, butanol and the like. Examples of glycol solvents include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, polyethylene glycol, polypropylene glycol and the like. Glycol ether solvents include ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, Examples include ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol monoisopropyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol monoisobutyl ether, ethylene glycol mono-t-butyl ether and the like. Examples of ester solvents include alkyl acetates (ethyl acetate, butyl acetate, etc.), methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, and the like. Examples of petroleum solvents include Solvesso #100 (manufactured by Exxon), Solvesso #150 (manufactured by Exxon) and the like. Chloroform etc. are illustrated as a haloalkane solvent. Examples of amide solvents include dimethylformamide and the like.

The substances exemplified as organic diluents and known organic diluents can be used alone or in combination of two or more. Among the components (E), since they have good miscibility with components having polysiloxane chains and components having polyalkylene glycol chains, (meth)acrylates having alkyl groups with 1 to 30 carbon atoms, and 3 carbon atoms (Meth) acrylate having an alicyclic structure of ~30, (meth) acrylate having an aromatic structure having 6 to 30 carbon atoms and one or more selected from ester solvents are preferable, and have 4 to 18 carbon atoms selected from (meth)acrylates having an alkyl group, (meth)acrylates having an alicyclic structure having 4 to 18 carbon atoms, (meth)acrylates having an aromatic structure having 6 to 18 carbon atoms, and ester solvents More preferably one or more types, (meth)acrylate having an alkyl group having 6 to 15 carbon atoms, (meth)acrylate having an alicyclic structure having 6 to 15 carbon atoms, aromatic having 6 to 18 carbon atoms (Meth)acrylate having a structure, and one or more selected from an ester solvent having an alkyl group having 1 to 10 carbon atoms, and a (meth)acrylate having an alkyl group having 8 to 12 carbon atoms, (Meth)acrylates having an alicyclic structure having 8 to 12 carbon atoms, (meth)acrylates having an aromatic structure having 6 to 12 carbon atoms, and 1 to 1 carbon atoms which may have an ether bond One or more selected from ester solvents having 10 alkyl groups are particularly preferable, and (meth)acrylates having an alkyl group having 10 to 12 carbon atoms, and (meth) having an alicyclic structure having 10 to 12 carbon atoms. ) acrylates, (meth)acrylates having an aromatic structure having 10 to 12 carbon atoms, and ester solvents having an alkyl group having 1 to 10 carbon atoms which may have an ether bond. is more particularly preferred, a (meth)acrylate having an alkyl group having 10 to 12 carbon atoms, a (meth)acrylate having an alicyclic structure having 10 to 12 carbon atoms, and an aromatic structure having 10 to 12 carbon atoms and one or more selected from (meth)acrylates having an alkyl group having 1 to 10 carbon atoms are even more particularly preferred.

The upper limit of the number of carbon atoms in component (E) is 30, 25, 20, 18, 15, 12, 10, 8, 6, 5, 4, 3, 2, etc., and the lower limit is 25, 20, 18. , 15, 12, 10, 8, 6, 5, 4, 3, 2, 1, and the like. In one embodiment, component (E) preferably has 1 to 30 carbon atoms.

The upper limit of the content ratio (mass ratio, [(E) component / water]) of component (E) and water is 25/75, 20/80, 15/85, 10/90, 5/95, 1/ 99, 0.5/99.5, etc., and the lower limits are 20/80, 15/85, 10/90, 5/95, 1/99, 0.5/99.5, 0.1/99 .9 and the like are exemplified. In one embodiment, the content ratio of component (E) to water (mass ratio, [(E) component/water]) is preferably about 0.1/99.9 to 25/75, and 0.5 /99.5 to 20/80 is even more preferable.

The upper limit of the content ratio of the organic diluent to the solid content of the aqueous emulsion composition of the present disclosure (mass ratio, [solid content of the aqueous emulsion composition of the present disclosure/organic diluent]) is 99/1, 95/5. , 90/10, 80/20, 70/30, 60/40, 50/50, 40/60, 30/70, 20/80, 10/90, 5/95, etc., and the lower limit is 95/ 5, 90/10, 80/20, 70/30, 60/40, 50/50, 40/60, 30/70, 20/80, 10/90, 5/95, 1/99, etc. . In one embodiment, the content ratio of the organic diluent to the solid content of the aqueous emulsion composition of the present disclosure (mass ratio, [solid content of the aqueous emulsion composition of the present disclosure/organic diluent]) is from 40/60 to About 99/1 is preferable, and about 50/50 to 99/1 is more preferable.

<Other agents that can be added>
The water-based emulsion composition of the present disclosure further contains binder resins other than the resins exemplified above (acrylic resins, urethane resins, polyester resins, epoxy resins, alkyd resins, etc.), emulsifiers, anti-slip agents, slip agents, Various additives such as antiseptics, rust inhibitors, pH adjusters, pigments, dyes, lubricants, leveling agents, catalysts, antifoaming agents, and photosensitizers (amines, quinones, etc.) can also be incorporated.

<Method for preparing aqueous emulsion composition>
To make the aqueous emulsion composition of the present disclosure,
(1) A method of using only the emulsion of component (A),
(2) A method of mixing an emulsion of component (A) with an emulsion containing components (B), (C), and (D);
(3) a method of mixing an emulsion of component (A) with an emulsion containing components (B) and (C);
(4) A method of mixing an emulsion of component (A) with component (C);
(5) a method of mixing an emulsion of component (A) and component (D);
(6) A method using an emulsion containing components (A), (B), (C), and (D) (7) an emulsion containing components (A) and (C), and (D) A method of mixing components and the like are exemplified. In these methods (1) to (7), it is also possible to add a leveling agent and component (E) as appropriate.
In addition, as a method for producing each emulsion, a method of adding water to the resin liquid (X) containing the (A) and / or (B) components and kneading at about 20 to 70 ° C., a resin liquid containing the (C) component ( A method of adding an emulsifier and water to Y) and kneading the mixture at about 20 to 70° C. is exemplified. (X) and (Y) may separately contain components (A), (B), (C), (D), (E), leveling agents, and various other additives. If each of the above components is water-soluble, they may be added after the emulsion is produced. Moreover, the water and emulsifier added during kneading may be added once before kneading, or may be added in multiple portions together with the addition during kneading.
An aqueous emulsion composition can be obtained by dispersing the obtained emulsion composition as it is or in water.

The molar ratio of the hydroxyl groups of the preferred component (a1), the hydroxyl groups of the component (a2), the hydroxyl groups of the component (a3), and the isocyanate groups of the component (a4) (hydroxyl groups of the component (a1)/hydroxyl groups of the component (a2)/( When adding component (a2) in an excess amount beyond the range of hydroxyl groups of component a3) / isocyanate groups of component (a4), the above preferred components (A), (B), and (C) Adjust the content of component (C) so that it is the sum of the contents of component (a2) and component (C) (in terms of solid content) in the total amount of 100% by mass (in terms of solid content), (6) or ( It is preferable to produce an emulsion by the method of 7) because it has good emulsifiability and can satisfactorily exhibit various properties in the present disclosure.

<Cured product and laminate>
The present disclosure also provides a cured product of the aqueous emulsion composition. The present disclosure also provides a laminate (also referred to as a “release film” in the present disclosure) including a substrate and a cured product of the aqueous emulsion composition. The present disclosure also provides a method for producing a laminate, which comprises a step of curing an aqueous emulsion composition coated on at least one side of a substrate with active energy rays and/or heat.

Examples of substrates to which the aqueous emulsion composition of the present disclosure is applied include glass substrates, metal substrates, plastic substrates, and the like. Examples of plastic substrates include thermoplastic plastic substrates, thermosetting plastic substrates, and the like. Examples of thermoplastic plastic substrates include general-purpose plastic substrates, engineering plastic substrates, and the like. Examples of general-purpose plastic substrates include olefin-based, polyester-based, acrylic-based, vinyl-based, polystyrene-based, and the like. Examples of olefin-based materials include polyethylene, polypropylene, norbornene, and the like. Examples of polyester-based materials include polyethylene terephthalate (PET) and polyethylene naphthalate (PEN). Examples of acrylic materials include polymethyl methacrylate (PMMA). Examples of vinyl-based materials include polyvinyl chloride, polyvinylidene chloride, and polyvinyl alcohol. Examples of polystyrene-based resins include polystyrene (PS) resin, styrene-acrylonitrile (AS) resin, styrene-butadiene-acrylonitrile (ABS) resin, and the like. Examples of engineering plastic substrates include general-purpose engineering plastics, super engineering plastics, and the like. Examples of general-purpose engineering plastics include polycarbonate and polyamide (nylon). Examples of super engineering plastics include polyetheretherketone (PEEK). Examples of thermosetting plastic substrates include polyimide, epoxy resin, and melamine resin. Examples of other plastic substrates include triacetyl cellulose resin and the like. Further, the base material may be subjected to surface treatment (such as corona discharge). In addition, another layer (for example, an easy-adhesion layer, an anchor layer, etc.) may be provided between one or both sides of the substrate and the layer formed by the aqueous emulsion composition of the present disclosure. The thickness of the base material is not particularly limited, and is usually about 1 to 200 μm.

Methods for coating the aqueous emulsion composition of the present disclosure on a substrate include roll coater coating, reverse roll coater coating, bar coater coating, Mayer bar coating, air knife coating, gravure coating, and reverse gravure coating. Examples include printing, offset printing, flexographic printing, and screen printing. Although the coating amount is not particularly limited, it is usually in the range where the mass after drying is 0.01 to 20 g/m ² , preferably 0.025 to 10 g/m ² , more preferably 0. .05 to 5 g/m ² . The film thickness of the cured product of the water-based emulsion composition of the present disclosure is about 0.05 to 10 μm.

As a method of curing by irradiation with active energy rays, high-pressure mercury lamps, ultra-high-pressure mercury lamps, carbon arc lamps, metal halide lamps, xenon lamps, chemical lamps, electrodeless discharge lamps, LEDs, etc., which emit light in the wavelength range of 150 nm or more and 450 nm or less. is used to irradiate at about 10 mJ/cm ² or more and 10,000 mJ/cm ² or less. Before the active energy ray irradiation, it may be dried by heating if necessary. After the active energy ray irradiation, heating may be performed as necessary for complete curing. The heating conditions are about 60 to 150° C. and about 1 second to 30 minutes, preferably 70 to 130° C. and about 5 seconds to 10 minutes. As a method of curing by heating, a temperature of about 150 to 250° C. and a time of about 1 second to 30 minutes are exemplified, and a temperature of about 170 to 220° C. and a time of about 30 seconds to 20 minutes are exemplified.

The laminate of the present disclosure may be subjected to curing treatment if necessary. Although the conditions are not particularly limited, they are about 20 to 50° C. for 1 to 24 hours. By carrying out like this, the solvent resistance of hardened|cured material becomes more favorable.

Since the cured product of the water-based emulsion composition of the present disclosure has excellent releasability, the water-based emulsion composition of the present disclosure can be used as a release coating agent. Therefore, a laminate containing a cured product of the release coating agent of the present disclosure (also referred to as a “release layer” in the present disclosure) and a substrate can be used as a release film. The release layer can exhibit light release and solvent resistance. Therefore, the release film can be coated with a material containing a large amount of an organic solvent, such as a casting solution for a resin molding or an inorganic slurry.

The release film of the present disclosure can be used as an adhesive tape or an adhesive tape by applying an adhesive layer on the opposite side of the release layer. In addition, the release film of the present disclosure includes adhesive tapes, adhesive tapes, double-sided tapes, adhesive labels, protective films (separators) for adhesive surfaces and adhesive surfaces such as stickers, as well as resin molded products, synthetic leather, decorative boards, carbon fiber It is also useful as a process film used in the manufacture of prepregs, electrical and electronic parts, and the like. The release film of the present disclosure includes a cured product capable of suppressing silicone migration. Therefore, it is used as a process film or process tape (e.g., separator, carrier film (tape), transfer film, protective tape, etc.) for the production of electrical and electronic materials, where the occurrence of defects due to migration of silicone from the cured product is particularly undesirable. Especially useful. In the present disclosure, the term "electrical/electronic materials" refers to parts that constitute a group of products having electronic circuits, such as personal computers, mobile phones, liquid crystal displays, refrigerators, automobiles, and the like.

In addition, since the release film of the present disclosure suppresses the formation of fine unevenness on the surface of the release layer, the unevenness on the surface of the release layer is not transferred to the material, and the surface state of the material is mirror-like and high quality. Therefore, it is useful for separators, carrier films (tapes), transfer films, protective tapes, and the like.

In addition, it is also conceivable to use it for various applications in which the effects of the aqueous emulsion composition of the present disclosure can be exhibited.

Specific examples of the present disclosure will be described below with reference to Examples, but the present disclosure is not limited to these examples. All parts and percentages in the examples are based on mass unless otherwise specified.

<Synthesis Example 1: Synthesis of (A-1)>
Into a reaction vessel equipped with a stirring device and a cooling pipe, 100.0 parts of an isocyanurate-modified form of hexamethylene diisocyanate (manufactured by Tosoh Corporation, trade name "Coronate HXR"), one-end hydroxyl group-containing polydimethylsiloxane (JNC Corporation ), trade name “Silaplane FM-0411”) 17.8 parts, polyethylene glycol monomethyl ether (manufactured by NOF Corporation, trade name “Uniox M-400”) 33.8 parts, polyethylene glycol monomethyl ether ( NOF Corporation, trade name "Uniox M-1000") 84.7 parts, 0.04 parts of 4-methoxyphenol, 161.9 parts of isobornyl acrylate, and 0.25 parts of tin octylate were charged. After that, the temperature in the system was raised to 70° C. over about 15 minutes. Then, the inside of the reaction system was kept at the same temperature for 1.5 hours, and then cooled to 60°C. Then, after adding 185.5 parts of pentaerythritol polyacrylate (manufactured by Toagosei Co., Ltd., trade name "Aronix M-305") having a hydroxyl value of 115 mgKOH/g and 0.13 parts of tin octylate, the mixture was stirred for about 15 minutes. Over time, the temperature in the system was raised to 75°C. Then, after holding the reaction system at the same temperature for 1 hour, 0.02 part of 4-methoxyphenol was charged and cooled to obtain urethane (meth)acrylate (A-1). (A-1) is a mixture with isobornyl acrylate.

<Synthesis Example 2: Synthesis of (A-2)>
Into a reaction vessel equipped with a stirring device and a cooling pipe, 100.0 parts of an isocyanurate-modified form of hexamethylene diisocyanate (manufactured by Tosoh Corporation, trade name "Coronate HXR"), one-end hydroxyl group-containing polydimethylsiloxane (JNC Corporation ), trade name “Silaplane FM-0411”) 17.8 parts, polyethylene glycol monomethyl ether (manufactured by NOF Corporation, trade name “Uniox M-400”) 33.8 parts, polyethylene glycol monomethyl ether ( 67.6 parts of NOF Corporation, trade name "Uniox M-1000"), 0.04 parts of 4-methoxyphenol, 162.2 parts of isobornyl acrylate, and 0.25 parts of tin octylate were charged. After that, the temperature in the system was raised to 70° C. over about 15 minutes. Then, the inside of the reaction system was kept at the same temperature for 1.5 hours, and then cooled to 60°C. Then, after adding 185.5 parts of pentaerythritol polyacrylate (manufactured by Toagosei Co., Ltd., trade name "Aronix M-305") having a hydroxyl value of 115 mgKOH/g and 0.13 parts of tin octylate, the mixture was stirred for about 15 minutes. Over time, the temperature in the system was raised to 75°C. Then, after holding the reaction system at the same temperature for 1 hour, 0.02 part of 4-methoxyphenol was charged and cooled to obtain urethane (meth)acrylate (A-2). (A-2) is a mixture with isobornyl acrylate.

<Synthesis Examples 3 to 5: Synthesis of (A-3) to (A-5)>
Urethane (meth)acrylates (A-3) to (A-5) were obtained through the same steps as in Synthesis Example 2 except that the formulations shown in Table 1 were used. Urethane (meth)acrylate (A-3) is a mixture with 2-EHA, urethane (meth)acrylate (A-4) is a mixture with butyl acetate, and urethane (meth)acrylate (A-5) is It is a mixture with propylene glycol monomethyl ether acetate.

<Synthesis Example 6: Synthesis of (A-6)>
Butyl acetate was distilled off from urethane (meth)acrylate (A-4) under reduced pressure to obtain urethane (meth)acrylate (A-6) containing no component (E).

<Comparative Synthesis Example 1: Synthesis of (A-C1)>
Into a reaction vessel equipped with a stirring device and a cooling pipe, 122.9 parts of an isocyanurate-modified form of hexamethylene diisocyanate (manufactured by Tosoh Corporation, trade name "Coronate HXR"), one-end hydroxyl group-containing polydimethylsiloxane (JNC Corporation ), trade name “Silaplane FM-0411”) 21.8 parts, polyethylene glycol monomethyl ether (manufactured by NOF Corporation, trade name “Uniox M-400”) 41.6 parts, polyethylene glycol monomethyl ether ( NOF Corporation, trade name "Uniox M-1000") 83.1 parts, 0.04 parts of 4-methoxyphenol, 120.0 parts of isobornyl acrylate, and 0.25 parts of tin octylate were charged. After that, the temperature in the system was raised to 70° C. over about 15 minutes. Then, the inside of the reaction system was kept at the same temperature for 1.5 hours, and then cooled to 60°C. After charging 30.0 parts of 2-propanol and 0.13 parts of tin octylate, the temperature in the system was raised to 75° C. over about 15 minutes. Then, after maintaining the reaction system at the same temperature for 1 hour, 0.02 part of 4-methoxyphenol was charged and cooled to obtain urethane (meth)acrylate (A-C1). (A-C1) is a mixture with isobornyl acrylate.

<Comparative Synthesis Example 2: Synthesis of (A-C2)>
14.6 parts of isophorone diisocyanate, one end hydroxyl group-containing polydimethylsiloxane (manufactured by JNC Corporation, trade name "Silaplane FM-0411") 20.7 parts, 4- After charging 0.15 parts of methoxyphenol, 120.0 parts of isobornyl acrylate, and 0.12 parts of tin octylate, the temperature in the system was raised to 70° C. over about 15 minutes. Then, the inside of the reaction system was kept at the same temperature for 1.5 hours, and then cooled to 60°C. Then, after adding 196.7 parts of PEG 1000 (manufactured by NOF Corporation, trade name “PEG #1000”) and 0.12 parts of tin octylate, the temperature in the system was raised to 70°C over about 15 minutes. The temperature was raised to Then, the inside of the reaction system was kept at the same temperature for 1.5 hours, and then cooled to 60°C. Then, after adding 67.4 parts of 1,1-(bisacryloyloxymethyl)ethyl isocyanate (manufactured by Showa Denko K.K., trade name "Karenzu BEI") and 0.06 part of tin octylate, the mixture was allowed to cool for about 15 minutes. to raise the temperature in the system to 75°C. Then, after holding the reaction system at the same temperature for 1 hour, 0.15 part of 4-methoxyphenol was charged and cooled to obtain urethane (meth)acrylate (A-C2). (A-C2) is a mixture with isobornyl acrylate.

<Comparative Synthesis Example 3: Synthesis of (A-C3)>
A urethane (meth)acrylate (A-C3) was obtained through the same steps as in Comparative Synthesis Example 2 except that the formulation described in the table was used. (A-C3) is a mixture with isobornyl acrylate.

<Comparative Synthesis Example 4: Synthesis of (A-C4)>
9.3 parts of isophorone diisocyanate, 13.2 parts of Silaprene FM-0411, 0.15 parts of 4-methoxyphenol, 120.0 parts of isobornyl acrylate, 0.12 parts of tin octylate, bifunctional polyester polyol (( Kuraray Co., Ltd., trade name "Kuraray Polyol P-1010") 233.7 parts, tin octoate 0.12 parts, Karenz BEI 43.1 parts, tin octoate 0.06 parts, 4-methoxyphenol 0 Urethane (meth)acrylate (A-C4) was obtained in the same manner as in Comparative Synthesis Example 2 using 0.15 parts. (A-C4) is a mixture with isobornyl acrylate.

<Comparative Synthesis Example 5: Synthesis of (A-C5)>
100 parts of Coronate HXR, 0.3 parts of tin octoate, 182 parts of FM-0411, dipentaerythritol penta/hexaacrylate (Toagosei After charging 347 parts of Aronix M-400 (trade name, manufactured by Co., Ltd.) and 629 parts of ethyl acetate, the temperature in the system was raised to about 70° C. over about 1 hour. Then, the reaction system was maintained at the same temperature for 3 hours, and after confirming that the isocyanate group had disappeared, the system was cooled to obtain a urethane acrylate oligomer (A-C5).

The meanings of the terms in Table 1 are as follows.
': indicates that it is a comparative component.
FM0411: Polydimethylsiloxane containing one terminal hydroxyl group (manufactured by JNC Corporation, trade name “Silaplane FM-0411”)
M305: Pentaerythritol polyacrylate having a hydroxyl value of 115 mgKOH/g (manufactured by Toagosei Co., Ltd., trade name “Aronix M-305”)
M400: dipentaerythritol penta/hexaacrylate (manufactured by Toagosei Co., Ltd., trade name “Aronix M-400”)
BEI: 1,1-(bisacryloyloxymethyl)ethyl isocyanate (manufactured by Showa Denko K.K., trade name “Karenzu BEI”)
YM400: Polyethylene glycol monomethyl ether (manufactured by NOF Corporation, trade name “Uniox M-400”)
YM1000: Polyethylene glycol monomethyl ether (manufactured by NOF Corporation, trade name “Uniox M-1000”)
PEG1000: Polyethylene glycol (manufactured by NOF Corporation, trade name “PEG#1000”)
PPG1000: Polypropylene glycol (manufactured by ADEKA Co., Ltd., trade name "ADEKA POLYETHER P-1000").
P-1010: Polyester polyol (manufactured by Kuraray Co., Ltd., trade name “Kuraray Polyol P-1010”)
HXR: isocyanurate modified form of hexamethylene diisocyanate (manufactured by Tosoh Corporation, trade name "Coronate HXR")
IPDI: isophorone diisocyanate IBOA: isobornyl acrylate IPA: 2-propanol EAC: ethyl acetate 2-EHA: 2-ethylhexyl acrylate BAC: butyl acetate PMA: propylene glycol monomethyl ether acetate

<Production Example 1-1: Production of emulsion (1-1)>
28.8 parts of urethane (meth)acrylate (A-1) and 43.2 parts of water are added to a reaction vessel equipped with a stirrer and a cooling tube, heated to 60° C. over 15 minutes, and kneaded for 1 hour. Thus emulsion (1-1) was obtained. (A-1) is a mixture of component (A2) and isobornyl acrylate, and 8.0 parts out of 28.8 parts is isobornyl acrylate.

<Production Examples 1-2 to 1-6 and Comparative Production Example 1-C1: Production of Emulsion (1-2) to Emulsion (1-6) and Comparative Emulsion (1-C1)>
Emulsions (1-2) to (1-6) and comparative emulsion (1-C1) were obtained through the same steps as in Production Example 1-1 except that the formulations shown in Table 2 were used. In addition, the (A) component is a mixture with the (E) component, and (A-1), (A-2), (A-3), (A-4), and (A-5) in Table 2. , (A-6), and (A-C1) are values obtained by subtracting the content of component (E) from the charge amount.

The meanings of the terms in Table 2 are as follows.
': indicates that it is a comparative component.
IBOA: isobornyl acrylate 2-EHA: 2-ethylhexyl acrylate BAC: butyl acetate PMA: propylene glycol monomethyl ether acetate

<Synthesis Example 3: Synthesis of (B-1)>
Into a reaction vessel equipped with a stirring device and a cooling pipe, 42.9 parts of an isocyanurate modified form of hexamethylene diisocyanate (manufactured by Tosoh Corporation, trade name "Coronate HXR"), polyethylene glycol monomethyl ether (manufactured by NOF Corporation) , trade name "Uniox M-1000") 50.7 parts, pentaerythritol polyacrylate having a hydroxyl value of 115 mgKOH / g (manufactured by Toagosei Co., Ltd., trade name "Aronix M-305") 66.3 parts, octyl After charging 0.04 part of tin acid and 0.09 part of 4-methoxyphenol, the temperature in the system was raised to 70° C. over about 15 minutes. Then, the inside of the reaction system was kept at the same temperature for 1.5 hours, and then cooled to 60°C. Then, after adding 28.8 parts of pentaerythritol polyacrylate (manufactured by Toagosei Co., Ltd., trade name "Aronix M-305") having a hydroxyl value of 115 mgKOH/g and 0.08 part of tin octylate, the mixture was stirred for about 15 minutes. Over time, the temperature in the system was raised to 75°C. Next, after holding the reaction system at the same temperature for 1 hour, 0.09 part of 4-methoxyphenol was charged and cooled to obtain urethane (meth)acrylate (B-1) having a solid content of 100%. .

<Production Example 2-1: Production of emulsion (2-1)>
In a reaction vessel equipped with a stirring device and a cooling pipe, (B-1) 100.5 parts, ditrimethylolpropane tetraacrylate (manufactured by Toagosei Co., Ltd., trade name "Aronix M-408") 50.3 parts, hydroxyl group 50.3 parts of pentaerythritol polyacrylate (manufactured by Toagosei Co., Ltd., trade name "Aronix M-933") having a value of 275 mg KOH / g, 1-hydroxycyclohexyl phenyl ketone (manufactured by IGM Resins, trade name "OMNIRAD 184") 20.3 parts were added, the temperature was raised to 80° C., and the mixture was mixed for 30 minutes. After that, it is cooled to 40° C., kneaded at 40° C. while adding 221.2 parts of water to obtain an emulsion with a solid content of 50%, and further diluted with 110.5 parts of water to a solid content of 40%. 1) was obtained.

<Production Examples 2-2 to 2-8, 2-10 and Comparative Production Examples 2-C1 to 2-C4: Emulsions (2-2) to (2-8), (2-10) and Comparative Emulsions (2- Production of C1) ~ (2-C4)>
Emulsions (2-2) to (2-8), (2-10) and comparative emulsions (2-C1) to (2) were obtained through the same steps as in Production Example 2-1 except that the formulations shown in the table were used. -C4). In the kneading step, water was added in an amount necessary for making the solid content 50%, and the remainder was added all at once to obtain an emulsion having a solid content of 40%.

<Production Example 2-9: Production of emulsion (2-9)>
In a reaction vessel equipped with a stirring device and a cooling pipe, (B-1) 122.9 parts, ditrimethylolpropane tetraacrylate (manufactured by Toagosei Co., Ltd., trade name "Aronix M-408") 66.4 parts, hydroxyl group 31.9 parts of pentaerythritol polyacrylate (manufactured by Toagosei Co., Ltd., trade name “Aronix M-305”) having a value of 115 mgKOH/g was added and mixed for 30 minutes. Thereafter, the temperature was raised to 40° C., and the mixture was kneaded at 40° C. while adding 331.8 parts of water to obtain emulsion (2-9).

<Production Example 2-11: Production of emulsion (2-11)>
60.5 parts of (B-1) and 12 mol of EO-modified dipentaerythritol hexaacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name "NK Ester A-DPH- 12E”) and 100.8 parts of 10-functional urethane acrylate (manufactured by Nippon Kayaku Co., Ltd., trade name “KAYARAD DPHA-40H”) were added, heated to 80° C. and mixed for 30 minutes. Thereafter, the mixture was cooled to 40° C. and kneaded at 40° C. while adding 201.6 parts of water to obtain emulsion (2-11).

The meanings of terms in Tables 3 and 4 are as follows.
TEGO: Product name "TEGORAD2200N" (manufactured by Evonik)
M408: Ditrimethylolpropane tetraacrylate (manufactured by Toagosei Co., Ltd., trade name “Aronix M-408”)
M933: Pentaerythritol polyacrylate having a hydroxyl value of 275 mgKOH/g (manufactured by Toagosei Co., Ltd., trade name “Aronix M-933”)
M306: Pentaerythritol polyacrylate having a hydroxyl value of 160 mgKOH/g (manufactured by Toagosei Co., Ltd., trade name “Aronix M-306”)
M920: Glycerin polyacrylate having a hydroxyl value of 240 mgKOH/g (manufactured by Toagosei Co., Ltd., trade name “Aronix M-920”)
M305: Pentaerythritol polyacrylate having a hydroxyl value of 115 mgKOH/g (manufactured by Toagosei Co., Ltd., trade name “Aronix M-305”)
DPH-12E: 12 mol EO-modified dipentaerythritol hexaacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name "NK Ester A-DPH-12E")
DPHA-40H: 10-functional urethane acrylate (manufactured by Nippon Kayaku Co., Ltd., trade name “KAYARAD DPHA-40H”)
184: 1-hydroxycyclohexylphenyl ketone (manufactured by IGM Resins, trade name “OMNIRAD 184”)
2959: 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-methylpropane (manufactured by IGM Resins, trade name “OMNIRAD 2959”)
907: 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one (manufactured by IGM Resins, trade name “OMNIRAD 907”)
754: Oxy-phenyl-acetic acid 2-[2-oxo-2-phenyl-acetoxy-ethoxy]-ethyl ester with oxy-phenyl-acetic acid 2-[2-hydroxy-ethoxy]-ethyl ester Mixture (manufactured by IGM Resins, trade name "OMNIRAD 754")
IBOA: isobornyl acrylate EAC: ethyl acetate

<Example 1: Water-based emulsion composition (1)>
72 parts of emulsion (1-1), 553 parts of emulsion (2-1), 5 parts of a leveling agent (manufactured by Nissin Chemical Industry Co., Ltd., trade name "OLFINE EXP.4200") are placed in a reaction vessel equipped with a stirring device, 375 parts of water was added and mixed for 30 minutes to obtain an aqueous emulsion composition (1) containing 25% active ingredient.

<Examples 2 to 37 and Comparative Examples 1 to 6: Aqueous emulsion compositions (2) to (37) and (C1) to (C6)>
Aqueous emulsion compositions (2) to (37) and (C1) to (C6) were obtained through the same steps as in Example 1 except that the formulations shown in the table were used.

<Performance evaluation (1): Solvent resistance test>
Each of the aqueous emulsion compositions (1) to (24), (26) to (37) and (C1) to (C6) was applied to a polyethylene terephthalate film (thickness: 100 μm) with a bar coater and dried at 80° C. for 1 minute. After that, active energy rays were irradiated (ultraviolet irradiation, illuminance: 520 mw/cm ² ) to obtain laminates (1) to (24), (26) to (37) and (C1) to (C6), respectively. Further, the aqueous emulsion composition (25) was applied to a polyethylene terephthalate film (thickness: 100 μm) with a bar coater and cured by heating at 180° C. for 10 minutes to obtain a laminate (25). A cotton swab impregnated with isopropanol, ethyl acetate, or toluene is rubbed against the surface of the cured product of each laminate and reciprocated 10 times, and the presence or absence of changes in the cured product is visually observed. evaluated. The film thickness of the cured product of the water-based emulsion composition and the cumulative amount of light (mJ/cm ² ) related to the active energy ray irradiation were the values shown in the table.
◯: There is no change in the cured coating film compared to before the test.
x: Scratches or whitening of the cured coating film, or exposure of the substrate is observed.

<Performance evaluation (2): peelability test>
Peelability was evaluated by the method of Example (6) acrylic adhesive peel strength of WO2014/109341. Specifically, it was evaluated by the following methods.
After leaving the laminate obtained in the same manner as in performance evaluation (1) for 3 hours without load, an adhesive tape having a width of 50 mm and a length of 150 mm (Nitto Denko Co., Ltd. No. 31B/ A two-layer structure of an acrylic pressure-sensitive adhesive and a polyester film) was press-bonded with a rubber roll to obtain a sample (polyethylene terephthalate film/cured product of aqueous emulsion composition/acrylic pressure-sensitive adhesive/polyester film). After that, the sample was cut into a width of 10 mm to obtain a sample for measuring separation strength. The peel strength of the peel strength measurement sample between the adhesive tape and the cured product of the aqueous emulsion composition was measured in a constant temperature room at 23 ° C. with a Tensilon universal tester (product name "RTC-1250A", A&D Co., Ltd. (manufactured). The peeling angle was 180° and the peeling speed was 300 mm/min.

<Performance evaluation (3): Surface unevenness suppression test (Sq)>
A laminate similar to that of performance evaluation 1 was observed with a paired scanning white light interference microscope (manufactured by Hitachi High-Tech Co., Ltd.), and the root mean square height Sq (nm) was measured, and then evaluated according to the following criteria.
4A: less than 1.5 nm 3A: 1.5 nm or more and less than 2.5 nm 2A: 2.5 nm or more and less than 7.5 nm A: 7.5 nm or more and less than 20.0 nm C: 20.0 nm or more

<Performance evaluation (4): Si migration test>
The element content ratio of the surface of the tape that was in contact with the surface of the cured product after the evaluation of the peelability test was measured using a scanning X-ray photoelectron spectrometer (product name “PHI5000VersaProbeIII”, manufactured by ULVAC-Phi, Inc.). bottom. The measured values were analyzed, and the Si element content ratio/C element content ratio was evaluated according to the following criteria.
2A: less than 4.5 A: 4.5 or more and less than 9.0 C: 9.0 or more

The meanings of the terms in Tables 5-9 are as follows.
The content of the emulsion in the table is a numerical value including water contained in the emulsion, and is not a solid content conversion.
EXP4200: trade name “OLFINE EXP4200” (manufactured by Nissin Chemical Industry Co., Ltd.)
SIL503A: trade name “Silface SAG-503A” (manufactured by Nissin Chemical Industry Co., Ltd.)
EXP4123: trade name “OLFINE EXP4123” (manufactured by Nissin Chemical Industry Co., Ltd.)
BYK331: Product name "BYK331" (manufactured by BYK)
DISP102: Product name "DISPERBYK-102" (manufactured by BYK)
TEGO2200: Product name "TEGORAD2200N" (manufactured by Evonik)
DYNOL607: trade name “Dynol 607” (manufactured by Nissin Chemical Industry Co., Ltd.)
FOM03009: N,N',N'',N'''-tetraacryloyltriethylenetetramine (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., trade name "FOM-03009")
FOM03011: photoradical initiator (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., trade name “FOM-03011”)

Claims (8)

Polysiloxane (A1) having a (meth)acryloyloxy group in a side chain, polysiloxane (a1) having a hydroxyl group, (meth)acrylate having a hydroxyl group (a2), polyethylene glycol having a hydroxyl group at one end (a3) and 3 An aqueous emulsion composition containing a (meth)acrylate (A) containing at least one selected from the group consisting of reactants (A2) of components containing a functional or higher polyisocyanate (a4). The aqueous system according to claim 1, comprising a urethane (meth)acrylate (B) which is a reaction product of a component containing a (meth)acrylate having a hydroxyl group (b1), a polyethylene glycol having a hydroxyl group (b2) and a polyisocyanate (b3). emulsion composition. 2. The aqueous emulsion composition according to claim 1, comprising at least one (C) selected from polyfunctional (meth)acrylate (c1) and polyfunctional (meth)acrylamide (c2). 2. The water-based emulsion composition according to claim 1, which contains a photopolymerization initiator (D). An aqueous emulsion composition according to claim 1, comprising an organic diluent (E). A release coating agent comprising the aqueous emulsion composition according to claim 1 . A cured product of the water-based emulsion composition according to claim 1 or the release coating agent according to claim 6. A laminate comprising the cured product according to claim 7 and a substrate.