JP2023059259A - Aqueous emulsion composition, cured product and laminate - Google Patents

Abstract

To provide a cured product having contamination resistance (mustard resistance) and a good appearance, a laminate including the cured product, and an aqueous emulsion composition capable of being stably stored at low temperature and capable of giving the cured product.SOLUTION: An aqueous emulsion composition comprises: a poly(meth)acrylate (A) having five or more (meth)acryloyl groups; a urethane (meth)acrylate (B) which derives from a rection of components comprising a (meth)acrylate (b1) having a hydroxy group, a polyisocyanate (b2) and a polyalkylene glycol (b3) having a hydroxy group; and a photopolymerization initiator (C). In the total amount of 100 mass% of the components (A), (B), and (C) (in terms of solid content), the content of the component (B) is 7-27 mass% (in terms of solid content) and the content of the component (C) is 1-20 mass% (in terms of solid content).SELECTED DRAWING: None

Description

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

For the purpose of protecting the surface of various molded products, etc. (e.g. walls, floors and ceilings of buildings, desks, electrical appliances (smartphones, refrigerators, etc.)), contain various resins on the surfaces of various molded products, etc. It is common to provide a cured product of the composition.

In Patent Document 1, a coating layer containing a fluorine-based polymer having an organosilane component and a silyl group is provided, and by improving the contact angle of liquid oil on the coating layer, the surface of various molded products etc. is removed from contaminants. It is written about protecting.

JP-A-2000-351941

Substances containing coloring components (e.g., mustard, hair dye, paint, etc.) adhere to various molded products, etc., and may stain and stain various molded products. is required. Here, Patent Document 1 only improves the contact angle of liquid oil, and after removing the substance containing the coloring component on the surface of various molded products, the coloring component does not remain on the various molded products. Not evaluated. Moreover, in order not to impair the appearance of various molded products, it is also necessary that the cured product itself does not have an abnormality such as discoloration. Furthermore, compositions containing various resins may be stored in various environments (for example, at low temperatures), and it is also important that they have stability in such environments.

The subject of the present disclosure is a cured product with good stain resistance (mustard resistance) and appearance, a laminate having the cured product, and a water-based emulsion that has good low-temperature storage stability and can obtain the cured product. It is to provide a composition.

As a result of intensive studies, the present inventors have found that the above problems can be solved by a given water-based emulsion composition, cured product and laminate. The present invention has been made to solve at least part of the above problems, and can be implemented as the following aspects or application examples.

（一般式（１）中、
＊^１は炭素原子との結合部位を示し、
＊^２は炭素原子又は水素原子との結合部位を示す。）
（項目２）
項目１に記載の水系エマルジョン組成物の硬化物。
（項目３）
項目２に記載の硬化物を有する積層体。 The following items are provided by this disclosure.
(Item 1)
Poly(meth)acrylate (A) having 5 or more (meth)acryloyl groups,
Urethane (meth)acrylate (B) which is a reaction product of components containing a (meth)acrylate having a hydroxyl group (b1), a polyisocyanate (b2) and a polyalkylene glycol having a hydroxyl group (b3), and general formula (1) A photopolymerization initiator (C) containing two or more of the represented structures and one or more alkyl groups other than the groups in the general formula (1)
including
The content (as solid content) of component (B) in the total amount of 100% by mass (as solid content) of components (A), (B), and (C) is 7 to 27% by mass,
The content of component (C) (in terms of solid content) is 1 to 20% by mass.
Aqueous emulsion composition.
General formula (1):

(In general formula (1),
* ¹ indicates the bonding site with the carbon atom,
* ² indicates a bonding site with a carbon atom or a hydrogen atom. )
(Item 2)
A cured product of the water-based emulsion composition according to Item 1.
(Item 3)
A laminate having the cured product according to Item 2.

The water-based emulsion composition provided by the present disclosure is excellent in low-temperature storage stability, and the cured product and laminate are excellent in stain resistance (mustard resistance) and appearance.

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. In the following, the constituent elements, manufacturing method, and the like of the present disclosure will be described in detail.

<(A) Component>
Component (A) is a poly(meth)acrylate having 5 or more (meth)acryloyl groups. In addition, the (A) component does not contain the (B) component.

(A) components include dipentaerythritol penta(meth)acrylate, tripentaerythritol hepta(meth)acrylate, and an acrylate having 16 to 20 (meth)acryloyl groups having a dendrimer structure (product name: Sirius- 501”, manufactured by Osaka Organic Chemical Industry Co., Ltd.).

Other (A) components are exemplified by one or more selected from urethane (meth)acrylates, ester (meth)acrylates, and epoxy (meth)acrylates.

As urethane (meth)acrylate,
(1) a reaction product of a polyol and a (meth)acrylate having an isocyanate group;
(2) a reaction product of a polyisocyanate and a (meth)acrylate having a hydroxyl group;
(3) a reaction product of a (meth)acrylate having an isocyanate group and a (meth)acrylate having a hydroxyl group; and (5) one or more selected from a reaction product of a prepolymer having a terminal isocyanate group, which is a reaction product of a polyol and a polyisocyanate, and a (meth)acrylate having a hydroxyl group.

Examples of polyols include one or more selected from dihydric alcohols, trihydric alcohols, tetrahydric alcohols, pentahydric alcohols, and hexahydric alcohols. Examples of dihydric alcohol include one or more selected from ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, neopentyl glycol, and dimer diol. Examples of trihydric alcohol include one or more selected from glycerin, trimethylolethane, and trimethylolpropane. As the tetrahydric alcohol, one or more selected from pentaerythritol and diglycerin are exemplified. Dipentaerythritol etc. are illustrated as a hexahydric alcohol.

As polyisocyanates, linear aliphatic diisocyanates (hexamethylene diisocyanate, etc.), branched aliphatic diisocyanates (trimethylhexamethylene diisocyanate, etc.), and alicyclic diisocyanates (dicyclohexylmethane diisocyanate, isophorone diisocyanate, 1,4-cyclohexane diisocyanate, hydrogenated xylene diisocyanate, hydrogenated tolylene diisocyanate, etc.).

Examples of hydroxyl-containing (meth)acrylates include hydroxyl-containing mono(meth)acrylates (2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 3-hydroxybutyl ( meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, etc.), and poly (meth) acrylates having hydroxyl groups (glycerin di (meth) acrylate, pentaerythritol tri (meth) acrylate, di Pentaerythritol penta(meth)acrylate, etc.) are exemplified.

Examples of (meth)acrylates having an isocyanate group include mono(meth)acrylates having an isocyanate group (2-isocyanatoethyl (meth)acrylate, etc.) and di(meth)acrylates having an isocyanate group (1,1-(bisacryloyl oxymethyl)ethyl isocyanate, etc.) are exemplified.

Examples of other urethane (meth)acrylates include aliphatic urethane (meth)acrylates having six (meth)acryloyl groups (product name “Miramer PU-610”, manufactured by Miwon Specialty Chemical Co.), and the like.

The upper limit of the number of (meth)acryloyl groups in component (A) is exemplified by 30, 25, 20, 18, 16, 15, 14, 13, 12, 11, 10, 9, 8, 7, 6, etc. , the lower limit is 25, 20, 18, 16, 15, 14, 13, 12, 11, 10, 9, 8, 7, 6, 5, and the like. In one embodiment, the number of (meth)acryloyl groups in component (A) is preferably about 5 to 30.

The upper limit of the molecular weight of component (A) is exemplified by 5,000, 4,000, 3,000, 2,000, 1,000, 500, 250, 100, etc., and the lower limit is 4,000, 3,000, 2,000, 1,000, 500, 250, 100, 50 and the like are exemplified. In one embodiment, the molecular weight of component (A) is preferably about 50 to 5,000. In the present disclosure, when simply describing "molecular weight", it refers to a value calculated on the basis of atomic weight.

The upper limit of the weight average molecular weight (Mw) of component (A) is exemplified by 5,000, 4,000, 3,000, 2,000, 1,000, 500, 250, 100, etc., and the lower limit is 4,000. , 3,000, 2,000, 1,000, 500, 250, 100, 50, and the like. In one embodiment, the weight average molecular weight (Mw) of component (A) is preferably about 50 to 5,000. In the present disclosure, the weight average molecular weight (Mw) is a polystyrene equivalent value obtained by gel permeation chromatography.

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) in the present disclosure is 89, 88, 87, 86, 85, 80, 75, 70, 65, 60, 55% by mass, etc., and the lower limit is 88, 87, 86, 85, 80, 75, 70, 65, 60, 55, 50% by mass etc. are exemplified. 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 components (A), (B), and (C) of the present disclosure is Preferably, it is about 50 to 89% by mass.

<(B) Component>
Component (B) is a urethane (meth)acrylate (B) which is a reaction product of a component containing a (meth)acrylate having a hydroxyl group (b1), a polyisocyanate (b2), and a polyalkylene glycol having a hydroxyl group (b3). be. Component (B) is exemplified by component (A) described in JP-A-2021-017592.

<(b1) component>
Examples of the component (b1) include one or more selected from glycerin (meth)acrylate having a hydroxyl group, pentaerythritol (meth)acrylate having a hydroxyl group, and polymethylolpropane (meth)acrylate having a hydroxyl group.

As glycerin (meth)acrylates having a hydroxyl group, glycerin mono(meth)acrylate, glycerin di(meth)acrylate, diglycerin di(meth)acrylate, diglycerin tri(meth)acrylate, triglycerin di(meth)acrylate, triglycerin tri( One or more selected from meth)acrylates and triglycerin tetra(meth)acrylates are exemplified.

Examples of pentaerythritol (meth)acrylates having a hydroxyl group include pentaerythritol mono (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) ) acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, tripentaerythritol di(meth)acrylate, tripentaerythritol tri(meth)acrylate, tripentaerythritol tetra(meth)acrylate, tripenta One or more selected from erythritol penta(meth)acrylate, tripentaerythritol hexa(meth)acrylate, and tripentaerythritol hepta(meth)acrylate, and the like are exemplified.

Examples of polymethylolpropane (meth)acrylate having a hydroxyl group include one or more selected from ditrimethylolpropane di(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, and trimethylolpropane di(meth)acrylate. be.

The (b1) component may be the same as the (meth)acrylate having a hydroxyl group described in the description of the (A) component.

Component (b1) is preferably pentaerythritol (meth)acrylate having a hydroxyl group, more preferably pentaerythritol tri(meth)acrylate, dipentaerythritol penta( It is one or more selected from meth)acrylates and mixtures of pentaerythritol tri(meth)acrylate and dipentaerythritol penta(meth)acrylate.

The upper limit of the number of (meth)acryloyl groups in component (b1) is 30, 25, 20, 18, 16, 15, 14, 13, 12, 11, 10, 9, 8, 7, 6, 5, 4 3 etc. are exemplified, and the lower limit is exemplified by 25, 20, 18, 16, 15, 14, 13, 12, 11, 10, 9, 8, 7, 6, 5, 4, 3, 2 etc. be. In one embodiment, the number of (meth)acryloyl groups in component (b1) is preferably about 2 to 30.

The upper limit of the molecular weight of component (b1) is 5,000, 4,000, 3,000, 2,000, 1,000, 500, 250, 100, etc., and the lower limit is 4,000, 3,000, 2,000, 1,000, 500, 250, 100, 50 and the like are exemplified. In one embodiment, the molecular weight of component (b1) is preferably about 50 to 5,000.

The upper limit of the content (in terms of solid content) of component (b1) in 100% by mass (in terms of solid content) of component (B) of the present disclosure is 80, 70, 60, 50, 40, 30, 20, 10, Examples include 5 mass %, and the lower limits include 70, 60, 50, 40, 30, 20, 10, 5, 1 mass % and the like. In one embodiment, the content of component (b1) in 100% by mass (in terms of solid content) of component (B) of the present disclosure (in terms of solid content) is excellent in curability and solvent resistance of the cured product. Therefore, it is preferably 5 to 80% by mass, more preferably 10 to 70% by mass.

<(b2) component>
(b2) components include linear aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, aromatic diisocyanates, biuret, isocyanurate, allophanate, and adduct of these diisocyanates, as well as biuret and isocyanurate , one or more selected from complexes obtained by reacting two or more selected from the group consisting of allophanate and adduct, and the like.

As linear aliphatic diisocyanate, one selected from methylene diisocyanate, ethylene diisocyanate, propylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, octamethylene diisocyanate, nonamethylene diisocyanate, and decamethylene diisocyanate The above etc. are illustrated.

Examples of branched aliphatic diisocyanates include trimethylhexamethylene diisocyanate.

Examples of alicyclic diisocyanates include one or more selected from isophorone diisocyanate, cyclohexylmethane diisocyanate, and norbornenemethane diisocyanate.

Examples of aromatic diisocyanates include one or more selected from diphenylmethane diisocyanate, phenylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, and naphthylene diisocyanate.

As a biuret form of diisocyanate, from the product names "Duranate 24A-100", "Duranate 22A-75P" (manufactured by Asahi Kasei Corp.), and the product name "Desmodur N3200A" (manufactured by Sumika Bayer Urethane Co., Ltd.) One or more selected types and the like can be mentioned.

As isocyanurate diisocyanates, the product names "Duranate TPA-100" and "Duranate TKA-100" (manufactured by Asahi Kasei Corporation), the product names "Coronate HXR" and "Coronate HX" (manufactured by Tosoh Corporation), and One or more selected from the product name "VESTANAT T1890/100" (manufactured by Evonik Japan Co., Ltd.) is exemplified.

As an allophanate form of diisocyanate, product name "Coronate 2793" (manufactured by Tosoh Corporation) is exemplified.

As diisocyanate adducts, product names "Takenate D-110N" and "Takenate D-160N" (manufactured by Mitsui Chemicals, Inc.), product names "Coronate L" and "Coronate HL" (manufactured by Tosoh Corporation), and One or more selected from the product name "Duranate P301-75E" (manufactured by Asahi Kasei Corp.) is exemplified.

Component (b2) may be the same as the polyisocyanate described in the description of component (A).

Component (b2) is preferably one or more selected from biuret, isocyanurate, allophanate, and adducts from the standpoint of excellent stain resistance and solvent resistance of the resulting cured product.

The upper limit of the number of isocyanate groups in component (b2) is exemplified by 10, 9, 8, 7, 6, 5, 4, 3, etc., and the lower limit is 9, 8, 7, 6, 5, 4, 3. , two, and the like. In one embodiment, the number of isocyanate groups in component (b2) is preferably about 2 to 10.

The upper limit of the molecular weight of component (b2) is 5,000, 4,000, 3,000, 2,000, 1,000, 500, 250, 100, etc., and the lower limit is 4,000, 3,000, 2,000, 1,000, 500, 250, 100, 50 and the like are exemplified. In one embodiment, the molecular weight of component (b2) is preferably about 50 to 5,000.

The upper limits of the molar ratio (NCO _(b2) /OH _(b1) ) between the isocyanate groups contained in the component (b2) and the hydroxyl groups contained in the component (b1) are 6.0, 5.5, 5.0, 4.5, 4.0, 3.5, 3.0, 2.5, 2.0, 1.5, etc. are exemplified, and the lower limits are 5.5, 5.0, 4.5, 4.0. , 3.5, 3.0, 2.5, 2.0, 1.5, 1.2, and the like. In one embodiment, the molar ratio (NCO _(b2) /OH _(b1) ) between the isocyanate groups contained in the component (b2) and the hydroxyl groups contained in the component (b1) is From the viewpoint of superiority, it is preferably about 1.2 to 6.0, more preferably about 1.5 to 3.0.

The upper limit of the content (in terms of solid content) of component (b2) in 100% by mass (in terms of solid content) of component (B) of the present disclosure is 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20% by mass, etc. are exemplified, and the lower limit is exemplified by 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15% by mass. In one embodiment, the content (in terms of solid content) of component (b2) in 100% by mass (in terms of solid content) of component (B) of the present disclosure is excellent in stain resistance and solvent resistance, It is preferably 15 to 75% by mass, more preferably 15 to 60% by mass.

<(b3) Component>
Component (b3) is a polyalkylene glycol having a hydroxyl group.

Examples of component (b3) include one or more selected from polyalkylene glycol, polyalkylene glycol monoalkyl ether, polyalkylene glycol mono(meth)acrylate, polyalkylene glycol monoallyl ether, and polyalkylene glycol monoacylate. be done.

As polyalkylene glycol, polyethylene glycol, polypropylene glycol, polybutylene glycol, polyether glycol having at least one structure of ethylene oxide/propylene oxide/butylene oxide block or random copolymer, polyoxytetramethylene 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 polyoxytetra Methylene glycol polyethylene glycol (block copolymer), polyethylene glycol polyoxytetramethylene glycol (random copolymer), polypropylene glycol polyoxytetramethylene glycol polypropylene glycol (block copolymer), polyoxytetramethylene glycol polypropylene glycol polyoxytetramethylene glycol (block copolymer) ), and one or more selected from polypropylene glycol, polyoxytetramethylene glycol (random copolymer), and the like.

As polyalkylene glycol monoalkyl ethers, polyethylene glycol derivatives (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 monooctyl 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, etc.), and one or more selected from polypropylene glycol derivatives (polypropylene glycol monomethyl ether, etc.).

Polyalkylene glycol mono(meth)acrylates such as polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, polyethylene glycol polypropylene glycol mono(meth)acrylate, poly(ethylene glycol tetramethylene glycol) mono(meth)acrylate, and poly(propylene glycol tetramethylene glycol) mono(meth)acrylate, and the like.

Examples of polyalkylene glycol monoallyl ether include one or more selected from polyethylene glycol monoallyl ether, polypropylene glycol monoallyl ether, and polyethylene glycol polypropylene glycol monoallyl ether.

Examples of polyalkylene glycol monoacylate include one or more selected from polyethylene glycol monolaurate, polyethylene glycol monostearate, and polyethylene glycol monooleate.

Component (b3) is preferably represented by the following general formula (2) from the viewpoint of excellent water dispersibility of the aqueous emulsion composition.

General formula (2):
H—(OCH ₂ CH ₂ ) _n —OR
(Wherein, R represents an alkyl group, an allyl group, a (meth)acryloyl group, or an acyl group, and n represents an integer of 3 to 25.)

Component (b3) is particularly preferably one or more selected from polyethylene glycol monomethyl ether and polyethylene glycol mono(meth)acrylate from the viewpoint of excellent water dispersibility of the aqueous emulsion composition.

The upper limit of the hydroxyl value of component (b3) is exemplified by 300, 250, 200, 150, 140, 130, 120, 110, 100, 90, 80, 70, 60, 50, 40, 30, 20 mgKOH/g. , the lower limit is exemplified by 250, 200, 150, 140, 130, 120, 110, 100, 90, 80, 70, 60, 50, 40, 30, 20, 10 mgKOH/g. In one embodiment, the hydroxyl value of component (b3) is preferably about 10 to 300 mgKOH/g, more preferably about 30 to 140 mgKOH/g, from the viewpoint of excellent water dispersibility. In the present disclosure, the hydroxyl value is a numerical value measured according to JIS K 1557 B method (phthalation method).

The upper limit of the number average molecular weight of component (b3) is exemplified by 3,000, 2,500, 2,000, 1,500, 1,000, 900, 800, 700, 600, 500, 400, 300, etc. The lower limit is exemplified by 2,500, 2,000, 1,500, 1,000, 900, 800, 700, 600, 500, 400, 300, 200 and the like. In one embodiment, the number average molecular weight of component (b3) is preferably about 200 to 3,000, more preferably about 200 to 3,000, from the viewpoint of excellent water dispersibility of the aqueous emulsion composition and stain resistance of the cured product. It is about 400 to 2,000. In addition, in this indication, a number average molecular weight is a polystyrene conversion value in the gel permeation chromatography method.

The upper limit of the content (in terms of solid content) of component (b3) in 100% by mass (in terms of solid content) of component (B) of the present disclosure is 50, 45, 40, 35, 30, 25, 20, 15, 10% by mass and the like are exemplified, and the lower limit is exemplified by 45, 40, 35, 30, 25, 20, 15, 10, 5% by mass and the like. In one embodiment, the content (in terms of solid content) of component (b3) in 100% by mass (in terms of solid content) of component (B) of the present disclosure is preferably 5 to 5 in terms of excellent water dispersibility. 50% by mass, more preferably 10 to 30% by mass. When the content of the component (b3) is 5% by mass or more, the water dispersibility is more excellent, and separation of the aqueous emulsion composition over time can be suppressed, which is preferable. Further, when the content of the component (b3) is 50% by mass or less, the crosslink density is high, the curability is more sufficient, and the obtained cured film has high stain resistance, which is preferable.

In component (B), the molar ratio (OH _(b1) /NCO _{(b2) /OH (b3)) of the hydroxyl group of component (b1), the isocyanate group of component (b2)} , and the hydroxyl group of component _(b3) is water From the standpoint of excellent dispersibility and hardness of the cured product, the ratio is preferably 0.1-0.9:1:0.1-0.9, more preferably 0.4-0.8:1:0.1. ~0.6.

The reactive components in component (B) may include components other than components (b1), (b2) and (b3) (hereinafter also referred to as “other components”). Other components are exemplified by compounds having at least one functional group capable of reacting with an isocyanate group in the molecule. A hydroxyl group, an amino group, etc. are illustrated as an isocyanate group and a reactive functional group.

The upper limit of the weight average molecular weight of component (B) is exemplified by 10,000, 9,000, 8,000, 7,000, 6,000, 5,000, 4,000, 3,000, 2,000, etc. 9,000, 8,000, 7,000, 6,000, 5,000, 4,000, 3,000, 2,000, 1,000 and the like are exemplified as the lower limit. In one embodiment, the weight average molecular weight of component (B) is preferably about 1,000 to 10,000 from the viewpoint of curability. In addition, in this indication, a weight average molecular weight is a polystyrene conversion value in the gel permeation chromatography method.

The upper limit of the number of (meth)acryloyl groups possessed by the component (B) is exemplified by 30, 25, 20, 15, 10, 8, 6, 4, 2, etc., and the lower limit is 25, 20, 15, 10. , 8, 6, 4, 2, 1, etc. are exemplified. In one embodiment, the number of (meth)acryloyl groups of component (B) is preferably 2 or more from the viewpoint of excellent curability.

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. in the presence of a catalyst at an appropriate reaction temperature (for example, 60 to 90° C.). Further, the order of reacting the components (b1), (b2) and (b3) is exemplified by a method of optionally mixing and reacting them, a method of mixing all the components together and reacting, and the like. As catalysts, organic tin catalysts (dibutyltin dilaurate, dioctyltin dilaurate, etc.), organic acid tin catalysts (tin octylate, etc.), organic titanium catalysts (titanium ethylacetoacetate, etc.), organic zirconium catalysts (zirconium tetraacetylacetonate, etc.), Organic iron catalysts (iron acetylacetonate, etc.) and the like are exemplified. The upper limit of the catalyst content (in terms of solid content) relative to the total amount of 100% by mass (in terms of solid content) of the components (b1), (b2) and (b3) of the present disclosure is 5, 4, 3, 2, 1 , 0.5, 0.1, 0.05, 0.01, 0.005% by mass, etc., and the lower limits are 4, 3, 2, 1, 0.5, 0.1, 0.05, 0.01, 0.005, 0.001% by mass and the like are exemplified.

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, etc. are exemplified, and the lower limits are 95/5, 90/10, 85/15, 80/20, 75/25, 70/30 , 65/35, 60/40, 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 60/40 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) in the present disclosure is 27, 26, 25, 20, 15, 10, 9, 8% by mass, etc. are exemplified, and the lower limit is exemplified by 26, 25, 20, 15, 10, 9, 8, 7% by mass, etc. In one embodiment, 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) of the present disclosure is Preferably, it is about 7 to 27% by mass.

<(C) Component>
Component (C) is a photopolymerization initiator (C) containing two or more structures represented by formula (1) and one or more alkyl groups other than the groups in formula (1).

（一般式（１）中、
＊^１は炭素原子との結合部位を示し、
＊^２は炭素原子又は水素原子との結合部位を示す。） General formula (1):

(In general formula (1),
* ¹ indicates the bonding site with the carbon atom,
* ² indicates a bonding site with a carbon atom or a hydrogen atom. )

(C) The upper limit of the number of structures represented by the general formula (1) present in one molecule of component (C) is exemplified by 10, 9, 8, 7, 6, 5, 4, 3, etc., and the lower limit is 9. , 8, 7, 6, 5, 4, 3, 2, and the like. In one embodiment, the number of structures represented by general formula (1) present in one molecule of component (C) is 2 or more, preferably 2 or more and 10 or less, more preferably 2 or more and 7 It is below. When the number of structures represented by the general formula (1) present in one molecule of component (C) is 1, the resistance to mustard deteriorates, which is not preferable. When the number of structures represented by the general formula (1) in one molecule of component (C) exceeds 10, it is not preferable because component (A) does not mix with other components.

Component (C) The upper limit of the number of alkyl groups other than the groups in formula (1) present in one molecule is 20, 18, 16, 14, 12, 10, 8, 6, 5, 4, 3, 2 and the like are exemplified, and the lower limits are exemplified by 18, 16, 14, 12, 10, 8, 6, 5, 4, 3, 2, 1 and the like. In one embodiment, the number of alkyl groups other than the groups in general formula (1) present in one molecule of component (C) is 1 or more, preferably 2 or more, more preferably 3. at least one. Taking structural formula (2) as an example, the number of alkyl groups other than the groups in general formula (1) present in one molecule of component (C) is three.

The upper limit of the number of carbon atoms of the alkyl group other than the group in the general formula (1) present in one molecule of component (C) is exemplified by 5, 4, 3, 2, etc., and the lower limit is 4, 3, 2, 1 and the like are exemplified. In one embodiment, the number of carbon atoms in the alkyl group other than the group in general formula (1) present in one molecule of component (C) is preferably 3 or less, more preferably 2 or less, and still more 1 is preferred.

(C) A component may be a commercial item. Examples of commercially available products include product names "ESACURE KIP 150" and "ESACURE ONE" (manufactured by IGM Resins).

The product name "ESACURE KIP 150" contains structural formula (1).

Structural formula (1):

The product name "ESACURE ONE" contains structural formula (2).

Structural formula (2):

That is, the component (C) of the present disclosure is a photopolymerization initiator (C ), preferably a photoinitiator (C) containing structural formula (1) and/or structural formula (2).

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

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 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, etc., and the lower limit is 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 etc. exemplified. 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 30/70 to 95/5. is preferred.

The upper limits 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) of the present disclosure are 20, 19, 18, 17, 16, 15, 14, 13, 12, 11, 10, 9, 8, 7, 6, 5, 4, 3, 2% by mass, etc., and the lower limit is 19, 18, 17, 16 , 15, 14, 13, 12, 11, 10, 9, 8, 7, 6, 5, 4, 3, 2, 1% by mass, and the like. 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) of the present disclosure is Preferably, it is about 1 to 20% by mass.

<(D) Component>
The aqueous emulsion composition of the present disclosure may contain a (meth)acrylate (D) having 4 or less (meth)acryloyl groups (also referred to as “(D) component” in the present disclosure).

The (D) component is exemplified by one or more selected from mono(meth)acrylates, di(meth)acrylates, tri(meth)acrylates, and tetra(meth)acrylates.

Mono(meth)acrylates include 1,4-cyclohexanedimethanol mono(meth)acrylate, β-carboxyethyl (meth)acrylate, isobornyl (meth)acrylate, ethoxylated phenyl (meth)acrylate, 2-(o-phenylphenoxy ) one or more selected from ethyl (meth) acrylate, docosyl (meth) acrylate, hydroxyethyl acrylate, 4-hydroxybutyl acrylate, methyl acrylate, ethyl acrylate, butyl acrylate, and glycerin mono (meth) acrylate, etc. be.

Di(meth)acrylates include dipropylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, tripropylene glycol di(meth)acrylate, PO-modified neopentyl glycol di(meth)acrylate, EO-modified Bisphenol A di(meth)acrylate, PEG400 di(meth)acrylate, PEG600 di(meth)acrylate, tricyclodecanedimethanol di(meth)acrylate, glycerin di(meth)acrylate, diglycerin di(meth)acrylate, triglycerin di( One or more selected from meth)acrylate, ditrimethylolpropane di(meth)acrylate, and trimethylolpropane di(meth)acrylate are exemplified.

Tri(meth)acrylates such as trimethylolpropane tri(meth)acrylate, trimethylolpropane ethoxytri(meth)acrylate, glycerin propoxy tri(meth)acrylate, pentaerythritol tri(meth)acrylate, diglycerin tri(meth)acrylate, One or more selected from triglycerin tri(meth)acrylate and ditrimethylolpropane tri(meth)acrylate are exemplified.

Tetra (meth) acrylate, one or more selected from pentaerythritol tetra (meth) acrylate, pentaerythritol alkoxytetra (meth) acrylate, pentaerythritol ethoxy tetra (meth) acrylate, and ditrimethylolpropane tetra (meth) acrylate, etc. are exemplified.

The upper limit of the number of (meth)acryloyl groups in component (D) is exemplified by 4, 3, 2, etc., and the lower limit is exemplified by 3, 2, 1, etc. In one embodiment, the number of (meth)acryloyl groups in component (D) is about 1 to 4.

The upper limit of the molecular weight of component (D) is 5,000, 4,000, 3,000, 2,000, 1,000, 500, 250, 100, etc., and the lower limit is 4,000, 3,000, 2,000, 1,000, 500, 250, 100, 50 and the like are exemplified. In one embodiment, the molecular weight of component (D) is preferably about 50 to 5,000.

The upper limit of the content ratio (mass ratio, solid content conversion, [(A) component/(D) component]) of component (A) and component (D) is 100/0, 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., and the lower limits are 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, 1/99, and the like. 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 1/99 to 100/0. is preferred.

The upper limit of the content ratio of component (B) to component (D) (mass ratio, in terms of solid content, [(B) component/(D) component]) is 100/0, 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., and the lower limits are 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, 1/99, and the like. In one embodiment, the content ratio (mass ratio, in terms of solid content, [(B) component/(D) component]) of component (B) and component (D) is about 1/99 to 100/0. is 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 100/0, 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., and the lower limits are 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, 1/99, 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 1/99 to 100/0. is 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) in the present disclosure are 20, 15, and 10. , 5, 4, 3, 2, 1, 0.5% by mass, etc., and the lower limit is exemplified by 15, 10, 5, 4, 3, 2, 1, 0.5, 0.1% by mass, etc. be done. In one embodiment, the content of component (D) relative to the total amount of 100% by mass (in terms of solid content) of components (A), (B), and (C) of the present disclosure (in terms of solid content) is preferably is about 0.1 to 20% by mass.

The total amount of (B) component and (D) component in the total amount of 100% by mass (solid content conversion) of (A) component, (B) component, (C) component, and (D) component of the present disclosure (solid content conversion ) is exemplified by 30, 25, 20, 15% by mass, etc., and its lower limit is exemplified by 25, 20, 15, 10% by mass, etc. In one embodiment, component (B) and component (D) account for 100% by mass (in terms of solid content) of the total amount of component (A), component (B), component (C), and component (D) of the present disclosure. The total amount of (in terms of solid content) is preferably about 10 to 30% by mass.

<Aqueous emulsion composition>
The water-based emulsion composition of the present disclosure may optionally contain a cross-linking agent, a leveling agent, an antifoaming agent, a thickener, a filler, an antioxidant, a waterproofing agent, and a film-forming aid, as long as the desired properties are not impaired. agent, pH adjuster, solvent (water-soluble organic solvent, water-insoluble organic solvent), emulsifier, dispersant, preservative, printability improver, viscosity adjuster, pigment, filler, oil-resistant agent, barrier agent, tackifier Agents and the like may also be included. Examples of water-soluble organic solvents include alcohols and ketones. Alcohols include methanol, ethanol, i-propanol, n-butanol, n-octanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether and the like. exemplified. Examples of ketones include acetone and methyl ethyl ketone. Examples of water-insoluble organic solvents include toluene and xylene. Although the aqueous emulsion composition of the present disclosure can contain a solvent, the aqueous emulsion composition of the present disclosure can be obtained without including a solvent, and considering the impact on the environment, the aqueous emulsion composition of the present disclosure is preferably Emulsion compositions do not contain solvents.

As a method for obtaining the aqueous emulsion composition of the present disclosure, a solventless phase inversion emulsification method and the like are exemplified. The solvent-free phase inversion emulsification method involves heating the components (A) and (C) to a certain temperature (about 70 to 120°C, preferably about 75 to 95°C) under pressure or normal pressure. After uniformly stirring and completely dissolving, component (B) and, if necessary, component (D) are kneaded, water is gradually added, phase inversion emulsification is performed, and emulsification is performed. be. Other components that are added as necessary are added to the system at the same time as the components (A) and (C), for example. The term "solvent-free" as used in the present disclosure means containing no solvent other than trace amounts of solvent derived from raw materials. Therefore, the upper limit of the amount (% by mass) of the solvent contained in the aqueous emulsion composition of the present disclosure when a trace amount of solvent derived from raw materials is included is 1, 0.5, 0.1, 0.05, 0.01, 0.001, etc. are exemplified, and the lower limits are 0.5, 0.1, 0.05, 0.01, 0.001, 0 .0001 and the like are exemplified. In one embodiment, the amount (% by weight) of solvent contained in the aqueous emulsion composition of the present disclosure is 1 or less.

The upper limit of the concentration (% by mass) of the aqueous emulsion composition of the present disclosure is , 15, 10, 5, etc., and the lower limits are 5, 1, etc. are exemplified. In one embodiment, the concentration (% by mass) of the aqueous emulsion composition of the present disclosure is preferably about 1 to 99% by mass.

The upper limit of the volume average particle size (μm) of the aqueous emulsion composition of the present disclosure is 10, 8, 6, 4, 2, 1.5, 1, 0.8, 0.5, 0.3, 0.1. , 0.05, etc., and the lower limits are 8, 6, 4, 2, 1.5, 1, 0.8, 0.5, 0.3, 0.1, 0.05, 0.01, etc. are exemplified. In one embodiment, the volume average particle size (μm) of the aqueous emulsion composition of the present disclosure is preferably about 0.01 to 10 μm. Most of the water-based emulsion compositions of the present disclosure are uniformly dispersed as particles of 1.5 μm or less, but from the viewpoint of storage stability at room temperature (25° C.), the volume average particle diameter is 1.0 μm or less. is preferably In the present disclosure, the volume-average particle size is the particle size at which the volume-based particle size distribution is 50% when the volume-based particle size distribution measured using a laser scattering method is integrated from the small particle size side. be.

The upper limit of the viscosity (mPa s) at a temperature of 25° C. and a concentration of 50% by mass of the water-based emulsion composition of the present disclosure is exemplified by 1,000, 750, 500, 250, 100, 75, 50, 25, 10, etc. , the lower limit is 750, 500, 250, 100, 75, 50, 25, 10, 5, and the like. In one embodiment, the viscosity (mPa·s) of the water-based emulsion composition of the present disclosure at a temperature of 25° C. and a concentration of 50% by mass is preferably about 5 to 1,000.

The upper limit of the pH of the water-based emulsion composition of the present disclosure at room temperature (25°C) is exemplified by 10, 9, 8, 7, 6, 5, 4, 3, etc., and the lower limit is 9, 8, 7, 6, 5, 4, 3, 2, etc. are exemplified. In one embodiment, the pH of the aqueous emulsion composition of the present disclosure is preferably about 2-10. The aqueous emulsion composition of the present disclosure may optionally contain inorganic acids (hydrochloric acid, sulfuric acid, phosphoric acid, etc.), alkanolamines (monoethanolamine, diethanolamine, diisopropanolamine, etc.), aliphatic amines (ethylamine, n-butylamine, etc.). , triethylamine, etc.), alkali metal hydroxides (potassium hydroxide, sodium hydroxide, etc.), alkaline earth metal hydroxides (calcium hydroxide, etc.), etc. may be added as appropriate to adjust the pH.

Examples of substrates to which the aqueous emulsion composition of the present disclosure is applied include glass substrates, plastic substrates, paper substrates, cloth substrates, rubber sheet substrates, foam sheet substrates, metal 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, and polynorbornene. Polyesters include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene succinate (PBS), polybutylene succinate adipate (PBSA), polybutylene adipate terephthalate (PBAT), polylactic acid (PLA), polyhydroxy Examples include alkanoic acid (PHA), polycaprolactone (PCL), and the like. 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, cellophane, plasticized starch, and the like. Japanese paper, kraft paper, glassine paper, woodfree paper, synthetic paper, top coat paper, etc., are exemplified as the paper substrate. Examples of the fabric base material include woven fabrics and non-woven fabrics obtained by spinning various fibrous materials alone or by blending them. Examples of rubber sheet substrates include natural rubber and butyl rubber. Examples of foam sheet substrates include foamed polyurethane and foamed polychloroprene rubber. Aluminum foil, copper foil, etc. are illustrated as a metal base material. Further, the base material may be subjected to surface treatment (such as corona discharge). Further, on one or both sides of the substrate, other layers (for example, an easy-adhesion layer, an anchor layer, etc.) may be provided between the cured product of the aqueous emulsion composition of the present disclosure.

The upper limit of the thickness of the substrate is exemplified by 4,000, 3,000, 2,000, 1,000, 500, 100, 90, 80, 70, 60, 50, 40, 30, 20, 10 μm, etc. The lower limit is exemplified by 3,000, 2,000, 1,000, 500, 100, 90, 80, 70, 60, 50, 40, 30, 20, 10, 5 µm. In one embodiment, the thickness of the substrate is preferably about 5-4,000 μm.

Laminates of the present disclosure can be manufactured by various known methods. Specifically, the aqueous emulsion composition of the present disclosure is applied to at least one side of a substrate, dried if necessary, and then irradiated with an active energy ray to obtain a laminate of the present disclosure (substrate/ It is possible to obtain a cured product of the aqueous emulsion composition of the present disclosure. Furthermore, the aqueous emulsion composition of the present disclosure is applied to the surface of the obtained laminate that is not coated with the aqueous emulsion composition of the present disclosure, and another substrate is laminated thereon, and then activated energy is applied. Laminates (substrate/cured product of the aqueous emulsion composition of the present disclosure/substrate/cured product of the aqueous emulsion composition of the present disclosure) can also be produced by irradiation with radiation.

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, the weight after drying is usually about 0.1 to 30 g/m ² , preferably 1 to 20 g/m ² . The film thickness of the cured product of the water-based emulsion composition of the present disclosure is about 2 to 20 μm.

An ultraviolet ray, an electron beam, etc. are illustrated as an active energy ray. Examples of the ultraviolet light source include an ultraviolet irradiation device having a xenon lamp, a high-pressure mercury lamp, and a metal halide lamp. Incidentally, the amount of light, the arrangement of the light source, the transport speed, etc. can be adjusted as necessary. For example, when a high-pressure mercury lamp is used, one lamp having a light intensity of about 80 to 160 W/cm is typically cured at a conveying speed of about 5 to 50 m/min. On the other hand, in the case of electron beams, an electron beam accelerator having an acceleration voltage of usually about 10 to 300 kV is used for curing at a conveying speed of about 5 to 50 m/min.

The cured product of the water-based emulsion composition of the present disclosure is preferably used for the outermost surface of various molded articles, but it can also be used in various applications where the effects of the water-based emulsion composition of the present disclosure can be exhibited. be.

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 solid content unless otherwise specified.

<Production Example 1: Synthesis of (B)-1>
In a reaction vessel equipped with a stirrer, a thermometer and a cooling tube, 42.9 parts of an isocyanurate modified form of hexamethylene diisocyanate (product name "Coronate HXR" manufactured by Tosoh Corporation), polyethylene glycol monomethyl ether (product name " Uniox M-1000", manufactured by NOF Corporation) 51.0 parts, a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (product name "Aronix M-305", manufactured by Toagosei Co., Ltd.) 63.5 0.04 part of tin octylate and 0.1 part of 4-methoxyphenol were charged, and then 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 charging 27.6 parts of a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (product name "Aronix M-305", manufactured by Toagosei Co., Ltd.) and 0.07 part of tin octylate, the mixture is 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, 0.1 part of 4-methoxyphenol was charged, cooled, and urethane acrylate (B)-1 (in the present disclosure, "(B)-1 A mixture (solid content: 100%) of pentaerythritol triacrylate and pentaerythritol tetraacrylate (D)-1 (also referred to as “(D)-1” in the present disclosure) was obtained.

The ratio of (B)-1 and (D)-1 was calculated by the following method.
(1) The NCO value (mmol/g) was calculated from the NCO % (21.85%) of Coronate HXR using the NCO molecular weight of 42.0.
(2) The hydroxyl values of Uniox M-1000 (hydroxyl value 56.1 mgKOH/g) and Aronix M-305 (hydroxyl value 115.0 mgKOH/g) were converted to mmol/g. Calculated by (hydroxyl value mgKOH/g)/56.1.
(3) The number of moles of NCO or hydroxyl groups contained in the charged amount of each component was calculated using the values (mmol/g) obtained in (1) and (2) above. The calculation formula was calculated by (amount of each component charged (g)×mmol/g of each component/1000).
(4) Subtract the number of moles of hydroxyl groups contained in Uniox M-1000 from the number of moles of NCO contained in Coronate HXR, which is the numerical value obtained in (3) above, and react Coronate HXR with Uniox M-1000. The number of moles of NCO remaining afterward was calculated.
(5) The number of moles of residual NCO (value obtained in (4) above) is multiplied by the molecular weight (298.29) of the reacting component (pentaerythritol triacrylate), and the residual NCO and the reacting component (pentaerythritol triacrylate) acrylate) weight (g) was calculated.
(6) The weight (g) of unreacted acrylate in Aronix M-305 was calculated by subtracting the value obtained in (5) above from the total charge (g) of Aronix M-305.
(7) The mass % of unreacted acrylate was calculated from the formula of numerical value obtained in (6) above/total charged weight (g)×100, and this was taken as the ratio of unreacted acrylate (D)-1.
(8) From the amount (g) of catalyst and polymerization inhibitor charged, the ratio of components not involved in the reaction was calculated. (0.17%)
(9) The ratio of urethane acrylate (B)-1 was calculated from 100%-(value obtained in (9) above)-(value obtained in (10) above).

<Example 1: Preparation of aqueous emulsion composition (1)>
Urethane acrylate (product name “DPHA-40H” manufactured by Nippon Kayaku Co., Ltd., number of (meth)acryloyl groups: 10) was added as component (A) to a flask equipped with a stirrer, thermometer and reflux condenser. 84.6 parts, 3.0 parts of the product name "Esacure KIP 150" (manufactured by IGM Resins) as the component (C) were added, and the mixture was uniformly stirred at 85°C for 1 hour to dissolve completely, and then ( After adding 12.4 parts of a mixture of B)-1 and (D)-1 and stirring uniformly, 13.6 parts of water was added while maintaining the temperature at 40°C, and the mixture was kneaded at 40°C for 1 hour. After that, 172.1 parts of water for adjusting the solid content was gradually added for emulsification to obtain an aqueous emulsion composition (1) having a non-volatile content of 35% by mass.

<Examples 2 to 8 and Comparative Examples 1 to 13: Preparation of aqueous emulsion compositions (2) to (8) and (C1) to (C13)>
Aqueous emulsion compositions (2) to (8) and (C1) to (C13) were obtained through the same steps as in Example 1 except that the formulations shown in the table were used.

<Evaluation Example 1: Production of Laminate (1)>
The water-based emulsion composition (1) was applied onto a substrate (ABS resin, product name “ABS (white)”, manufactured by Nippon Test Panel Co., Ltd., 2 mm thick) so that the film thickness of the cured product was about 13 μm. It was applied with a #20 bar coater and dried at 60° C. for 10 minutes. Next, ultraviolet rays are irradiated (200 mW/cm ² , 1000 mJ/cm ² ) with an ultraviolet curing device (product name “UBT-080-7A/BM”, manufactured by Multiply Co., Ltd., high-pressure mercury lamp 600 mJ/cm ² ), A laminate (1) was obtained.

<Evaluation Examples 2 to 8 and Comparative Evaluation Examples 1 to 13: Production of laminates (2) to (8) and (C1) to (C13)>
Laminates (2)-( 8) and (C1) to (C13) were obtained.

<Performance evaluation (1): mustard test>
Laminates (1) to (8) and (C1) to (C13) are coated with mustard (product name “S&B mustard”, manufactured by SB Foods Co., Ltd.) and placed in a constant temperature and humidity chamber at 60°C and 95Rh%. It was allowed to stand inside for 24 hours. The mustard was washed off, and the color difference (ΔE94) from the uncoated mustard was measured under the following conditions.
(Measurement condition)
Spectral color difference meter: product name “SE6000” (manufactured by Nippon Denshoku Industries Co., Ltd.)
Mode: Transparent Normal standard white plate: SE37913A

<Performance evaluation (2): Appearance test>
The color difference (ΔE94) between the cured products of the laminates (1) to (8) and (C1) to (C13) and the substrate in the portion not coated with the water-based emulsion composition was measured using the same performance evaluation (1). Measured under conditions.

<Performance evaluation (3): Low temperature storage stability test>
The aqueous emulsion compositions (1) to (8) and (C1) to (C13) were stored at 4° C. for 90 days, and the presence or absence of precipitates in the aqueous emulsion compositions was checked and evaluated according to the following evaluation criteria.
Good: No precipitates in the emulsion.
x: Precipitates are present in the emulsion.

The meanings of the terms in the table are as follows.
The content in the table is a numerical value in terms of solid content.
UA: urethane acrylate (product name "DPHA-40H", manufactured by Nippon Kayaku Co., Ltd.)
DPHA: dipentaerythritol penta/hexaacrylate (product name "Aronix M-400", manufactured by Toagosei Co., Ltd.)
PETA: pentaerythritol tri/tetraacrylate (product name "Aronix M-305", manufactured by Toagosei Co., Ltd.)
RE-1000L: Surfactant (product name "Aminoion RE-1000L", manufactured by Nippon Nyukazai Co., Ltd.)
Esa One: Product name “Esacure ONE” (manufactured by IGM Resins)
Esa 150: Product name "Esacure KIP 150" (manufactured by IGM Resins)
Omni 2959: 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-methylpropane (product name “Omnirad 2959”, manufactured by IGM Resins, photopolymerization having one structure of general formula (1) initiator)
Omni 127: 2-hydroxy-1-(4-(4-(2-hydroxy-2-methylpropionyl)benzyl)phenyl)-2-methylpropan-1-one (product name "Omnirad 127", manufactured by IGM Resins , a photopolymerization initiator having two structures of the general formula (1))
Omni 907: 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one (product name "Omnirad 907", manufactured by IGM Resins)
Omni 379: 2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholin-4-yl-phenyl)butan-1-one (product name "Omnirad 379", manufactured by IGM Resins)
Omni TPO: 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (product name "Omnirad TPO", manufactured by IGM Resins)
OmniTPO-L: phenyl-(2,4,6-trimethylbenzoyl)-phosphinic acid ethyl ester (product name "Omnirad TPO-L", manufactured by IGM Resins)
Luna 100: 2-hydroxy-2-methylpropiophenone (product name “Lunacure 100”, manufactured by DKSH Japan Co., Ltd.)
TR-305: 1-[4-(phenylthio)phenyl]-3-cyclopentylpropane-1,2-dione-2-(o-benzoyloxime) (product name “TR-PBG-305”, manufactured by TRONLY)

Claims (3)

Poly(meth)acrylate (A) having 5 or more (meth)acryloyl groups,
Urethane (meth)acrylate (B) which is a reaction product of components containing a (meth)acrylate having a hydroxyl group (b1), a polyisocyanate (b2) and a polyalkylene glycol having a hydroxyl group (b3), and general formula (1) A photopolymerization initiator (C) containing two or more of the represented structures and one or more alkyl groups other than the groups in the general formula (1)
including
The content (as solid content) of component (B) in the total amount of 100% by mass (as solid content) of components (A), (B), and (C) is 7 to 27% by mass,
The content of component (C) (in terms of solid content) is 1 to 20% by mass.
Aqueous emulsion composition.
General formula (1):

(In general formula (1),
* ¹ indicates the bonding site with the carbon atom,
* ² indicates a bonding site with a carbon atom or a hydrogen atom. ) A cured product of the aqueous emulsion composition according to claim 1 . A laminate comprising the cured product according to claim 2 .