JP7497954B2 - Acrylic curable resin composition, paint, cured product, and coating material for civil engineering and construction - Google Patents

Description

The present invention relates to an acrylic curable resin composition containing an acrylic component, a paint, a cured product, and a coating material for civil engineering and construction.

2. Description of the Related Art Conventionally, acrylic curable resin compositions have been used as coating materials by applying them to floors, walls, road pavement surfaces, and the like, and then curing them, because they have excellent low-temperature curing properties, weather resistance, and chemical resistance.
However, acrylic curable resin compositions have a characteristic odor due to low molecular weight monomers such as methyl methacrylate, etc. Therefore, acrylic curable resin compositions with reduced odor have been proposed by using monomers with high molecular weights or monomers with high boiling points.
For example, Patent Document 1 proposes a curable resin composition containing a (meth)acrylate having a heterocycle. However, the curable resin composition described in Patent Document 1 does not provide a coating film with sufficient surface hardness, and therefore, in particular when the cured coating film is used as a topcoat layer, the stain resistance may be reduced.
Patent Document 2 proposes a curable resin composition containing a polymer having a polymerizable double bond and having 75 mass% or more of methyl methacrylate units. However, the coating film formed from the curable resin composition described in Patent Document 2 sometimes has insufficient impact resistance.

JP 2012-241155 A JP 2015-25101 A

The present invention aims to provide an acrylic curable resin composition and coating material that can give a cured product that has both stain resistance and impact resistance. The present invention also aims to provide a cured product and a coating material for civil engineering and construction that have both stain resistance and impact resistance.

The present invention includes any one of the following aspects [1] to [7].
[1] A monofunctional (meth)acrylate (A) having a cyclic structure,
(B) a (meth)acrylic polymer containing 20% by mass or more of a (meth)acrylic monomer unit;
a polyfunctional (meth)acrylate (C) comprising at least one of a difunctional (meth)acrylate represented by the following chemical formula (1) and a polyfunctional (meth)acrylate having a functionality of 3 or more and an acrylic equivalent of 170 or less;
(D) a polyfunctional (meth)acrylate other than the component (C);
and a reducing agent (E),
An acrylic curable resin composition comprising:
CH ₂ ═C(R ¹ )COO—(R ² —O—) _n —OC(R ¹ )C═CH ₂ ... (1)
(In chemical formula (1), R ¹ is H or CH ₃ , R ² is an alkylene or hydroxyalkylene having 1 to 12 carbon atoms, and n is 1 or 2.)
[2] With respect to the total 100% by mass of the components (A), (B), (C) and (D),
30 to 80% by mass of component (A),
5 to 30 mass% of component (B),
1 to 30 mass% of component (C),
Contains 1 to 30 mass% of component (D),
Relative to a total of 100 parts by mass of the components (A), (B), (C) and (D),
The acrylic curable resin composition according to [1], comprising 0.1 to 10 parts by mass of component (E).
[3] The acrylic curable resin composition according to [1] or [2], wherein the component (A) is a monofunctional (meth)acrylate having at least one cyclic structure selected from the group consisting of a furan ring, a hydrofuran ring, a pyran ring, a hydropyran ring, an aromatic ring, and an alicyclic structure.
[4] The acrylic curable resin composition according to any one of [1] to [3], wherein the component (B) is a (meth)acrylic polymer having a polymerizable double bond.
[5] A coating material comprising the acrylic curable resin composition according to any one of [1] to [4].
[6] A cured product obtained by curing the acrylic curable resin composition according to any one of [1] to [4] or the coating material according to [5].
[7] A coating material for civil engineering and construction comprising the cured product according to [6].

The acrylic curable resin composition and coating material of the present invention can give a cured product having both stain resistance and impact resistance.
The cured product and the coating material for civil engineering and construction of the present invention have both stain resistance and impact resistance.

The present invention will be described in detail below.
In the present invention, "(meth)acrylic" is a general term for acrylic and methacrylic. "(meth)acrylate" is a general term for acrylate and methacrylate. "(meth)acryloyl group" is a general term for acryloyl group and methacryloyl group.
The "cured product" refers to a product obtained by curing an acrylic curable resin composition.

<Acrylic curable resin composition>
One embodiment of the acrylic curable resin composition of the present invention (hereinafter, abbreviated as "resin composition") contains the following components (A), (B), (C), (D), and (E). Component (A): a monofunctional (meth)acrylate having a cyclic structure. Component (B): a (meth)acrylic polymer. Component (C): a specific polyfunctional (meth)acrylate described below. Component (D): a polyfunctional acrylate other than component (C).
Component (E): Reducing Agent Hereinafter, each component contained in the resin composition of this embodiment will be described.

[Component (A)]
The (A) component is a monofunctional (meth)acrylate having a cyclic structure in the molecule. By adjusting the content of the (A) component, the viscosity of the resin composition, the mechanical strength of the cured product, and the flash point temperature can be adjusted. The (A) component may be used alone or in combination of two or more types.
Of the components (A), monofunctional (meth)acrylates having at least one cyclic structure selected from the group consisting of a furan ring, a hydrofuran ring, a pyran ring, a hydropyran ring, an aromatic ring, and an alicyclic structure are preferred in terms of reducing odor.

Specific examples of the component (A) are shown below.
(Meth)acrylates having a furan ring: furyl (meth)acrylate, furfuryl (meth)acrylate, and the like.
(Meth)acrylates having a hydrofuran ring: tetrahydrofuryl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, caprolactone-modified tetrahydrofurfuryl (meth)acrylate, and the like.
(Meth)acrylates having a pyran ring: pyranyl (meth)acrylate, etc.
(Meth)acrylates having a hydropyran ring: dihydropyranyl (meth)acrylate, tetrahydropyranyl (meth)acrylate, dimethyldihydropyranyl (meth)acrylate, dimethyltetrahydropyranyl (meth)acrylate, and the like.
(Meth)acrylates having an aromatic ring: phenyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, phenoxypolyethylene glycol (meth)acrylate, nonylphenoxypolyethylene glycol (meth)acrylate, phenoxypropyl (meth)acrylate, phenoxypolypropylene glycol (meth)acrylate, nonylphenylcarbitol (meth)acrylate, nonylphenylcarbitol (meth)acrylate, nonylphenolpolyethylene glycol (meth)acrylate, nonylphenolpolypropylene glycol (meth)acrylate, (meth)acryloyloxyethyl phthalate, phenylphenoxyethyl (meth)acrylate, phenoxybenzyl (meth)acrylate, phenylbenzyl (meth)acrylate, naphthyl (meth)acrylate, (1-naphthyl)methyl (meth)acrylate, and the like.
(Meth)acrylates having an alicyclic structure: cyclohexyl (meth)acrylate, dicyclopentenyl (meth)acrylate, 2-dicyclopentenoxyethyl (meth)acrylate, isobornyl (meth)acrylate, and the like.
Of the components (A), (meth)acrylates having a hydrofuran ring, a hydropyran ring, an aromatic ring, or an alicyclic structure are more preferred, and those having a molecular weight in the range of 130 to 300 are even more preferred.
Among the (meth)acrylates having a hydrofuran ring, a hydropyran ring, an aromatic ring, or an alicyclic structure and having a molecular weight in the range of 130 to 300, at least one selected from the group consisting of tetrahydrofurfuryl (meth)acrylate, caprolactone-modified tetrahydrofurfuryl (meth)acrylate, dimethyldihydropyranyl (meth)acrylate, dimethyltetrahydropyranyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, cyclohexyl (meth)acrylate, dicyclopentenyl (meth)acrylate, 2-dicyclopentenoxyethyl (meth)acrylate, and isobornyl (meth)acrylate is particularly preferred.

The content of component (A) in the resin composition of this embodiment is preferably 30 to 80% by mass, more preferably 35 to 75% by mass, and even more preferably 40 to 70% by mass, relative to 100% by mass of the total of components (A), (B), (C), and (D). The higher the content of component (A) in the resin composition, the lower the viscosity and the easier it is to work with, for example, during painting. The lower the content of component (A) in the resin composition, the higher the contents of components (B), (C), and (D), and the more the stain resistance and impact resistance of the cured product can be improved.

[(Component B)]
The (meth)acrylic polymer which is the component (B) is a polymer containing 20% by mass or more of a (meth)acrylic monomer unit.
Component (B) is a component that imparts mechanical strength, and the viscosity of the resin composition can be adjusted by the content of component (B).
The component (B) may be used alone or in combination of two or more types.

The (meth)acrylic monomer means a monomer having a (meth)acryloyl group. The "unit" means a repeating unit constituting a polymer. The (meth)acrylic monomer may be a monofunctional monomer having one (meth)acryloyl group, or a polyfunctional monomer having two or more (meth)acryloyl groups. In terms of increasing compatibility in the resin composition, the (meth)acrylic monomer is preferably a monofunctional monomer.
Examples of monofunctional monomers include (meth)acrylates having a carboxy group, (meth)acrylates having a hydroxy group, alkyl (meth)acrylates, (meth)acrylates having a cyclic structure, alkoxy (meth)acrylates, and other monofunctional (meth)acrylates.
Examples of polyfunctional monomers include difunctional (meth)acrylates having two (meth)acryloyl groups, trifunctional (meth)acrylates having three (meth)acryloyl groups, tetrafunctional (meth)acrylates having four (meth)acryloyl groups, pentafunctional (meth)acrylates having five (meth)acryloyl groups, and hexafunctional (meth)acrylates having six (meth)acryloyl groups.
The (meth)acrylic monomer unit contained in the component (B) may be of one type, or of two or more types.

Specific examples of the monofunctional monomer are shown below.
(Meth)acrylates having a carboxy group: (meth)acrylic acid, 2-(meth)acryloyloxyethyl succinate, 2-(meth)acryloyloxyethyl maleate, 2-(meth)acryloyloxyethyl phthalate, 2-(meth)acryloyloxyethyl hexahydrophthalate, and the like.
(Meth)acrylates having a hydroxy group: 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, and the like.
Alkyl (meth)acrylates: methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, i-butyl (meth)acrylate, t-butyl (meth)acrylate, pentyl (meth)acrylate, heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, n-nonyl (meth)acrylate, isononyl (meth)acrylate, decyl (meth)acrylate, lauryl (meth)acrylate, tridecyl (meth)acrylate, stearyl (meth)acrylate, and the like.
(Meth)acrylates containing a cyclic structure: cyclohexyl (meth)acrylate, dicyclopentenyl (meth)acrylate, 2-dicyclopentenoxyethyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, adamantyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, phenoxypolyethylene glycol (meth)acrylate acrylate, nonylphenoxy polyethylene glycol (meth)acrylate, phenoxy polypropylene glycol (meth)acrylate, phenylphenyl (meth)acrylate, phenylphenoxyethyl (meth)acrylate, phenoxybenzyl (meth)acrylate, phenylbenzyl (meth)acrylate, naphthyl (meth)acrylate, (1-naphthyl)methyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, glycidyl (meth)acrylate, (meth)acryloylmorpholine, and the like.
Alkoxy (meth)acrylates: methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, and the like.
Other monofunctional (meth)acrylates: 3-(meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropyltriethoxysilane, 2-(meth)acryloyloxyethyl acid phosphate, trifluoroethyl (meth)acrylate, and heptadecafluorodecyl (meth)acrylate.

Specific examples of the polyfunctional monomer are shown below.
Bifunctional (meth)acrylates: alkylene glycol di(meth)acrylates such as ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, etc.; polyalkylene glycol di(meth)acrylates such as polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, polybutylene glycol di(meth)acrylate, etc.; neopentyl glycol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, polycarbonate diol di(meth)acrylate, polyester diol di(meth)acrylate, ethoxylated bisphenol A di(meth)acrylate, propoxylated bisphenol A di(meth)acrylate, 9,9-bis(4-(meth)acryloyloxyethoxyphenyl)fluorene, urethane di(meth)acrylate, etc.
Trifunctional (meth)acrylates: trimethylolpropane tri(meth)acrylate, ethoxylated isocyanuric acid tri(meth)acrylate, ε-caprolactone-modified tris((meth)acryloxyethyl)isocyanurate, and the like.
Tetrafunctional (meth)acrylates: ditrimethylolpropane tetra(meth)acrylate, etc.
Pentafunctional (meth)acrylates: dipentaerythritol penta(meth)acrylate, and the like.
Hexafunctional (meth)acrylates: dipentaerythritol hexa(meth)acrylate, and the like.

The component (B) may contain other monomer units in addition to the (meth)acrylic monomer units.
The other monomer may be any monomer that is copolymerizable with the (meth)acrylic monomer, and examples of the other monomer include aromatic vinyl monomers such as styrene and α-methylstyrene; vinyl cyanide monomers such as acrylonitrile; and vinyl ester monomers such as vinyl acetate.
The content of the (meth)acrylic monomer unit in the (B) component is preferably 50% by mass or more, more preferably 80% by mass or more, in terms of further improving the impact resistance of the cured product. The upper limit of the content of the (meth)acrylic monomer unit in the (B) component is not limited, and may be 100% by mass.

The polymerization method for obtaining component (B) is not particularly limited, and known methods such as solution polymerization, suspension polymerization, emulsion polymerization, and partial polymerization can be applied. Among the above polymerization methods, suspension polymerization is preferred because it is easy to control the polymerization reaction and to easily separate the obtained polymer.

Preferred specific examples of the component (B) include at least one selected from the group consisting of polymethyl methacrylate, polyethyl methacrylate, polybutyl methacrylate, a copolymer composed of methyl methacrylate units and n-butyl methacrylate units, and a copolymer composed of methyl methacrylate units and n-butyl acrylate units.
Among the preferable (B) components, in terms of increasing the transparency of the cured product, polymethyl methacrylate, a copolymer composed of methyl methacrylate units and n-butyl methacrylate units, and a copolymer composed of methyl methacrylate units and n-butyl acrylate units are preferable.
Among the preferable components (B), a (meth)acrylic polymer having a polymerizable double bond is preferable in terms of achieving higher mechanical strength.
The polymerizable double bond means, for example, a double bond involved in a radical polymerization reaction of a vinyl group, an allyl group, a (meth)acryloyl group, etc. If the component (B) has a polymerizable double bond, it can react with the (meth)acryloyl groups of the components (A), (C) and (D), and therefore the mechanical strength of the cured product can be further improved.

The (meth)acrylic polymer having a polymerizable double bond has an acrylic monomer unit and also has a polymerizable double bond.
Examples of the acrylic monomer unit include an alkyl (meth)acrylate unit, other monofunctional acrylic monomer units, polyfunctional acrylic monomer units, (meth)acrylic acid units, etc. Among the acrylic monomer units, an alkyl (meth)acrylate unit is preferred, and a methyl methacrylate unit is more preferred.
The (meth)acrylic polymer having a polymerizable double bond preferably contains 40% by mass or more, more preferably 50% by mass or more, of methyl methacrylate units. The more methyl methacrylate units there are, the higher the heat durability of the cured product becomes.

The method for producing the acrylic polymer having a polymerizable double bond is not particularly limited, but an example of a preferred method for producing the acrylic polymer having a polymerizable double bond is shown below.
In the first-stage reaction, one or more kinds of acrylic monomers (b1) are copolymerized with an acrylic monomer (b2) having a first functional group that is involved in an esterification reaction described below to obtain a precursor copolymer (B') having the first functional group.
Next, in the second stage reaction, an acrylic monomer (b3) having a second functional group and a double bond that undergoes an esterification reaction with the first functional group to generate a bond is added to the precursor copolymer (B'). This causes the first functional group of the precursor copolymer (B') to react with the second functional group of the acrylic monomer (b3) to form an ester. After the ester formation, the double bond derived from the acrylic monomer (b3) remains. Therefore, the ester formation reaction can introduce a polymerizable double bond into the precursor copolymer (B'), and an acrylic polymer having a polymerizable double bond can be obtained.

Specific examples of the acrylic monomer (b1) include alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, i-butyl (meth)acrylate, t-butyl (meth)acrylate, sec-butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate; and cycloalkyl (meth)acrylates such as isobornyl (meth)acrylate and cyclohexyl (meth)acrylate. The acrylic monomer (b1) may be used alone or in combination of two or more kinds.
Examples of the combination of the first functional group and the second functional group include a carboxy group and a glycidyl group, a hydroxy group and an isocyanate group, etc. When the combination of the first functional group and the second functional group is a combination of a carboxy group and a glycidyl group, it is preferable to use (meth)acrylic acid as the acrylic monomer (b2) and glycidyl (meth)acrylate as the acrylic monomer (b3).

As a method for producing an acrylic polymer having a polymerizable double bond, the following method is preferred.
In the first stage reaction, one or more of the acrylic monomers (b1) and (meth)acrylic acid are suspension polymerized to obtain a precursor copolymer (B') having a carboxy group. In the second stage reaction, the obtained precursor copolymer (B') is added to the component (A) to obtain a solution (S), and glycidyl (meth)acrylate is added to this solution (S). In the solution (S), the carboxy group of the precursor copolymer (B') and the glycidyl group of the glycidyl (meth)acrylate are reacted to form an ester. As a result, glycidyl (meth)acrylate is added to the precursor copolymer (B') to obtain an acrylic polymer having a polymerizable double bond.

In the first stage reaction, the polymerization temperature during suspension polymerization is preferably in the range of 70 to 98° C., and the polymerization time is preferably about 2 to 5 hours.
The preferred composition of the monomers polymerized in the first-stage reaction is 90 to 99.5% by mass of methyl methacrylate [component (b1)], 0 to 9% by mass of the acrylic monomer other than methyl methacrylate [component (b1)], and 0.5 to 7% by mass of (meth)acrylic acid [component (b2)]. More preferably, the content of (meth)acrylic acid [component (b2)] is 1 to 4% by mass.

The suspension used in the first stage reaction for suspension polymerization is preferably an aqueous suspension using water as a dispersion medium, and a dispersant is preferably added to the aqueous suspension.
The dispersant is not particularly limited, and examples thereof include poorly water-soluble inorganic compounds, nonionic polymers, and anionic polymers.
Specific examples of the dispersant are shown below.
Poorly water-soluble inorganic compounds: calcium phosphate, aluminum hydroxide, silica, etc.
Nonionic polymers: polyvinyl alcohol, polyethylene oxide, cellulose derivatives, etc.
Anionic polymers: poly(meth)acrylic acid alkali metal salts, alkali metal salts of (meth)acrylic acid and methyl (meth)acrylate copolymers, etc.
The amount of the dispersant used is preferably in the range of 0.005 to 5% by mass, and more preferably in the range of 0.01 to 1% by mass, relative to 100% by mass of the aqueous suspension.
The aqueous suspension used in the suspension polymerization preferably contains an electrolyte such as sodium carbonate, sodium sulfate, or manganese sulfate. By containing an electrolyte in the aqueous suspension, the dispersion stability of the acrylic monomers (b1), (b2) and the precursor copolymer (B') can be improved. The amount of the electrolyte used is not particularly limited.

In the suspension polymerization, it is preferable to use a polymerization initiator. Examples of the polymerization initiator include organic peroxides and azo compounds.
Examples of organic peroxides include benzoyl peroxide, lauroyl peroxide, methyl ethyl ketone peroxide, tert-butyl peroxybenzoate, cumene hydroperoxide, cyclohexanone peroxide, dicumyl peroxide, and bis(4-tert-butylcyclohexyl)peroxydicarbonate.
Examples of the azo compound include 2,2'-azobisisobutyronitrile, 2,2'-azobis-2-methylbutyronitrile, and the like.
The polymerization initiator may be used alone or in combination of two or more kinds.
The amount and method of adding the polymerization initiator are not particularly limited.

In the suspension polymerization, it is preferable to use a chain transfer agent, which makes it possible to easily control the polymerization reaction of the acrylic monomers (b1) and (b2).
As the chain transfer agent, a thiol compound is preferably used, and examples of the thiol compound include alkyl mercaptan, aromatic mercaptan, and alkyl thioglycolate.
Examples of the alkyl mercaptan include t-butyl mercaptan, n-octyl mercaptan, and n-dodecyl mercaptan.
Examples of aromatic mercaptans include thiophenol and thionaphthol.
Examples of the alkyl thioglycolate include thioglycolic acid and octyl thioglycolate.
The amount and method of adding the chain transfer agent are not particularly limited.

The glass transition temperature of the precursor copolymer (B') obtained in the first stage reaction is preferably 80 to 155°C, more preferably 80 to 110°C. If the glass transition temperature of the precursor copolymer (B') is 155°C or lower, the solubility of the precursor copolymer (B') obtained in the first stage reaction can be improved. If the glass transition temperature of the precursor copolymer (B') is 80°C or higher, the durability when heat is applied can be improved. The glass transition temperature of the precursor copolymer (B') is a value determined by a differential scanning calorimeter (hereinafter referred to as "DSC").

The reaction temperature in the second stage reaction is preferably 90 to 95° C., and the reaction time is preferably about 1 to 4 hours.
In the second stage reaction, it is preferable to add 100 parts by mass of the precursor copolymer (B') to 100 to 200 parts by mass of the component (A). It is also preferable to react 0.9 to 1.2 moles, and more preferably 1.0 to 1.1 moles, of glycidyl (meth)acrylate [component (b3)] with 1 mole of the (meth)acrylic acid [component (b2)] used in the first stage reaction.

In the second stage reaction, the reaction of the carboxyl group contained in the precursor copolymer (B') with the glycidyl group of the glycidyl (meth)acrylate can be confirmed by the fact that the acid value of the (B) component having a double bond is lower than the value estimated from the (meth)acrylic acid used in the first stage reaction.
The acid value (unit: mgKOH/g) of the polymer (B) obtained by the second-stage reaction is preferably not more than 1, more preferably not more than 0.5. The acid value in this specification is a value determined by dissolving the polymer in toluene and titrating it with a 0.1 N ethanol solution of potassium hydroxide using phenolphthalein as an indicator.

In the second step, in order to promote the reaction between the first functional group and the second functional group, it is preferable to use an esterification catalyst. Examples of the esterification catalyst include amine compounds, quaternary ammonium salts, phosphorus compounds, etc.
An example of the amine compound is triethylamine.
Examples of the quaternary ammonium salt include tetraethylammonium chloride and tetrabutylammonium bromide.
An example of the phosphorus compound is triphenylphosphine.
The esterification catalyst may be used alone or in combination of two or more kinds. The amount of the esterification catalyst to be added is not particularly limited.
A polymerization inhibitor may be added before the second stage reaction, which can improve the stability of the second stage reaction.
Examples of the polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, 2,6-di-t-butyl-4-methylphenol, etc. The polymerization inhibitor may be used alone or in combination of two or more kinds. The amount of the polymerization inhibitor to be added is not limited.

The weight average molecular weight (hereinafter referred to as " _Mw ") of component (B) is preferably in the range of 5,000 to 500,000, and more preferably in the range of 10,000 to 200,000. When the _Mw of component (B) is 5,000 or more, the strength of the cured product is better, and when it is 500,000 or less, the workability when handling the resin composition is good.
In this specification, _Mw is a molecular weight measured by dissolving a resin sample in a solvent (tetrahydrofuran) and measuring the molecular weight by gel permeation chromatography (hereinafter referred to as "GPC") in terms of polystyrene.

The content of the (B) component in the resin composition of this embodiment is preferably 5 to 30% by mass, more preferably 5 to 25% by mass, and even more preferably 10 to 25% by mass, relative to 100% by mass of the total of the (A), (B), (C) and (D) components. The higher the content of the (B) component in the resin composition, the more the impact resistance of the cured product can be improved. The lower the content of the (B) component in the resin composition, the lower the viscosity of the resin composition, improving workability such as painting.

[Component (C)]
The polyfunctional (meth)acrylate as component (C) is at least one of a bifunctional (meth)acrylate represented by the following chemical formula (1) [component (C1)] and a tri- or higher functional polyfunctional (meth)acrylate having an acrylic equivalent of 170 or less [component (C2)]:
CH ₂ ═C(R ¹ )COO—(R ² —O—) _n —OC(R ¹ )C═CH ₂ (1)
In the above chemical formula (1), ^R1 is H or _{CH3 .} ^R2 is an alkylene or hydroxyalkylene having 1 to 12 carbon atoms. n is 1 or 2.
Component (C) is a component that improves the surface hardness of the cured product, thereby improving the stain resistance. By using components (C) and (D) in combination, a tough cured product can be obtained.
The component (C) may be used alone or in combination of two or more types.

The structure of the alkylene or hydroxyalkylene having 1 to 12 carbon atoms for R ² in the component (C1) may be any of linear, branched, and cyclic structures, as well as structures that combine these.
Examples of the alkylene include ethylene, propylene, butylene, pentylene, hexylene, octylene, decylene, and dodecylene.
Examples of hydroxyalkylene include oxyethylene, oxypropylene, oxybutylene, oxypentylene, oxyhexylene, oxyoctylene, oxydecylene, and oxydodecylene.

Specific examples of the component (C1) are shown below.
Examples of the (C1) component in which R ² is alkylene include ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, 1,3-butylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,5-pentanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, 1,9-nonanediol diacrylate, 1,10-decanediol diacrylate, neopentyl glycol di(meth)acrylate, cyclohexanedimethanol di(meth)acrylate, 3-methyl-1,5-pentanediol di(meth)acrylate, tricyclodecane dimethanol dimethacrylate, diethylene glycol di(meth)acrylate, and dipropylene glycol di(meth)acrylate.
Examples of the component (C1) in which ^R2 is a hydroxyalkylene include trimethylolpropane di(meth)acrylate, glycerin dimethacrylate, and 2-hydroxy-3-acryloyloxypropyl methacrylate.

The acrylic equivalent of the (C2) component is 170 or less, preferably 165 or less, and more preferably 160 or less. The acrylic equivalent is a value calculated by the formula: molecular weight of a polyfunctional (meth)acrylate having a (meth)acryloyl group/number of functional groups of the (meth)acryloyl group. If the acrylic equivalent of the (C2) component exceeds 170, the stain resistance of the cured product may decrease.
Specific examples of the component (C2) include trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexaacrylate, and tris(2-acryloyloxyethyl)isocyanurate.

Among the (C) components, ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, 1,3-butylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,5-pentanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, 1,9-nonanediol diacrylate, 1,10-decanediol diacrylate, neopentyl glycol di(meth)acrylate, and cyclohexanedimethanol di(meth)acrylate are preferred because of their excellent curing properties. At least one selected from the group consisting of 3-methyl-1,5-pentanediol di(meth)acrylate, tricyclodecane dimethanol dimethacrylate, diethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexaacrylate, and tris(2-acryloyloxyethyl)isocyanurate is preferred.

The content of component (C) in the resin composition of this embodiment is preferably 1 to 30% by mass, more preferably 5 to 25% by mass, and even more preferably 5 to 20% by mass, relative to 100% by mass of the total of components (A), (B), (C), and (D). The higher the content of component (C) in the resin composition, the more the stain resistance of the cured product can be improved. Reducing the amount of component (D) relative to the total of components (C) and (D) and increasing the amount of component (C) relatively can improve the stain resistance of the cured product.

[Component (D)]
The component (D) is a polyfunctional (meth)acrylate other than the component (C). The component (D) is a component that improves the impact resistance of the cured product, and by using the component (D) in combination with the component (C), a tough cured product can be obtained.
The component (D) may be used alone or in combination of two or more types.

Specific examples of the component (D) include polyalkylene glycol di(meth)acrylate, ethoxylated neopentyl glycol di(meth)acrylate, propoxylated neopentyl glycol di(meth)acrylate, polyester diol di(meth)acrylate, ethoxylated bisphenol A di(meth)acrylate, propoxylated bisphenol A di(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, propoxylated trimethylolpropane tri(meth)acrylate, and ethoxylated isocyanuric acid tri(meth)acrylate. , propoxylated isocyanuric acid tri(meth)acrylate, ε-caprolactone-modified tris((meth)acryloxyethyl)isocyanurate, ethoxylated glycerin tri(meth)acrylate, propoxylated glycerin tri(meth)acrylate, ethoxylated pentaerythritol tetra(meth)acrylate, ethoxylated dipentaerythritol hexa(meth)acrylate, propoxylated dipentaerythritol hexa(meth)acrylate, urethane (meth)acrylate, polyester (meth)acrylate, epoxy (meth)acrylate, and the like.
Specific examples of polyalkylene glycol di(meth)acrylates include triethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, and polybutylene glycol di(meth)acrylate.
Of the (D) components, at least one selected from the group consisting of polyalkylene glycol di(meth)acrylates (particularly, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, polybutylene glycol di(meth)acrylate, etc.), ethoxylated bisphenol A di(meth)acrylate, propoxylated bisphenol A di(meth)acrylate, urethane (meth)acrylate, polyester (meth)acrylate, and epoxy (meth)acrylate is preferred, in terms of good compatibility with other components.
The molecular weight of component (D) is preferably from 250 to 10,000 in order to achieve an appropriate viscosity.

The content of the (D) component in the resin composition of this embodiment is preferably 1 to 30% by mass, more preferably 5 to 25% by mass, and even more preferably 5 to 20% by mass, relative to 100% by mass of the total of the (A), (B), (C) and (D) components. The higher the content of the (D) component in the resin composition, the more the impact resistance of the cured product can be improved. By reducing the (C) component relative to the total of the (C) and (D) components and increasing the (D) component relatively, the impact resistance of the cured product can be improved.

[Component (E) and Curing Agent (F)]
The resin composition of this embodiment is cured by the polymerization proceeding through radical polymerization.
In this embodiment, radicals are generated by a redox polymerization initiator that combines the reducing agent (E) and the curing agent (F) made of an organic peroxide, which will be described later. The redox polymerization initiator allows the radicals to be generated quickly by reducing the curing agent (F) with the component (E). Therefore, by including the component (E) in the resin composition of this embodiment, the resin composition can be cured quickly when the curing agent (F) is added.
However, when the curing agent (F) is added to the resin composition of this embodiment, curing starts immediately. Therefore, it is preferable to add the curing agent (F) immediately before curing the resin composition.
Examples of the component (E) include pyridine, aliphatic amines, heterocyclic amines, aromatic amines, metal soaps, and thiourea compounds.
The component (E) may be used alone or in combination of two or more types.

Specific examples of the component (E) are shown below.
Aliphatic amines: triethanolamine, diethylenetriamine, etc.
Heterocyclic amines: phenylmorpholine, piperidine, etc.
Aromatic amines: aniline and its derivatives, p-toluidine, m-toluidine, N-substituted-p-toluidine, N,N-substituted-p-toluidine, 4-(N,N-substituted amino)benzaldehyde, and the like.
Examples of the aniline derivatives include N,N-dimethylaniline, N,N-diethylaniline, N,N-bis(hydroxyethyl)aniline, and diethanolaniline.
An example of the N-substituted p-toluidine is N-ethyl-m-toluidine.
Examples of N,N-substituted-p-toluidines include N,N-dimethyl-p-toluidine, N,N-diethyl-p-toluidine, N,N-di(2-hydroxyethyl)-p-toluidine, N,N-di(2-hydroxypropyl)-p-toluidine, ethylene oxide adducts of N,N-di(2-hydroxyethyl)-p-toluidine or N,N-di(2-hydroxypropyl)-p-toluidine, and propylene oxide adducts of N,N-di(2-hydroxyethyl)-p-toluidine or N,N-di(2-hydroxypropyl)-p-toluidine.
Examples of 4-(N,N-substituted amino)benzaldehyde include 4-(N,N-dimethylamino)benzaldehyde, 4-[N,N-bis(2-hydroxyethyl)amino]benzaldehyde, and 4-(N-methyl-N-hydroxyethylamino)benzaldehyde.
Metal soaps: cobalt naphthenate, copper naphthenate, copper neodecanoate, copper versatate, manganese naphthenate, cobalt 2-ethylhexanoate, nickel 2-ethylhexanoate, cobalt acetylacetonate, zinc acetylacetonate, aluminum acetylacetonate, iron acetylacetonate, vanadyl acetylacetonate, vanadium acetylacetonate, and the like.
Thiourea compounds: thiourea, ethylenethiourea, N,N'-dimethylthiourea, N,N'-diethylthiourea, N,N'-dipropylthiourea, N,N'-di-n-butylthiourea, N,N'-dilaurylthiourea, N,N'-diphenylthiourea, trimethylthiourea, 1-acetyl-2-thiourea, 1-benzoyl-2-thiourea, and the like.
Among the components (E), aromatic amines are preferred, and aromatic tertiary amines are more preferred from the viewpoint of increasing the reactivity and curability of the resin composition.

Among the above-mentioned examples, the aromatic tertiary amine is N,N-dimethylaniline, N,N-diethylaniline, N,N-bis(hydroxyethyl)aniline, diethanolaniline, N,N-dimethyl-p-toluidine, N,N-diethyl-p-toluidine, N,N-di(2-hydroxyethyl)-p-toluidine, N,N-di(2-hydroxypropyl)-p-toluidine, N,N-di(2-hydroxyethyl)-p-toluidine or N,N-di These include an ethylene oxide adduct of N,N-di(2-hydroxyethyl)-p-toluidine or a propylene oxide adduct of N,N-di(2-hydroxypropyl)-p-toluidine, 4-(N,N-dimethylamino)benzaldehyde, 4-[N,N-bis(2-hydroxyethyl)amino]benzaldehyde, and 4-(N-methyl-N-hydroxyethylamino)benzaldehyde.
Among the aromatic tertiary amines, N,N-dimethyl-p-toluidine, N,N-diethyl-p-toluidine, N,N-di(2-hydroxyethyl)-p-toluidine, and N,N-di(2-hydroxypropyl)-p-toluidine are particularly preferred because they can enhance the reactivity and curability of the resin composition.
The aromatic tertiary amine is not limited to the p (para) form, but may be an o (ortho) form or an m (meta) form.

Component (F) is a curing agent comprising an organic peroxide.
Examples of the component (F) include ketone peroxides, peroxyketals, hydroperoxides, dialkyl peroxides, diacyl peroxides, peroxydicarbonates, and peroxyesters.
The component (F) may be used alone or in combination of two or more types.

Specific examples of the component (F) are shown below.
Ketone peroxides: methyl ethyl ketone peroxide, etc.
Peroxyketals: 1,1-di(t-hexylperoxy)-3,3,5-trimethylcyclohexane, 1,1-di(t-hexylperoxy)cyclohexane, 1,1-di(t-butylperoxy)cyclohexane, and the like.
Hydroperoxides: 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, p-menthane hydroperoxide, and the like.
Dialkyl peroxides: dicumyl peroxide, di-t-butyl peroxide, etc.
Diacyl peroxides: dilauroyl peroxide, dibenzoyl peroxide, and the like.
Peroxydicarbonates: di(4-t-butylcyclohexyl) peroxydicarbonate, di(2-ethylhexyl) peroxydicarbonate, and the like.
Peroxy esters: t-butylperoxy-2-ethylhexanoate, t-hexylperoxyisopropyl monocarbonate, t-butylperoxybenzoate, and the like.
Among the above-mentioned (F) components, ketone peroxides, peroxyketals, hydroperoxides, diacyl peroxides, and peroxydicarbonates are preferred, and dibenzoyl peroxide is more preferred, because they provide excellent curing properties for the resin composition.

As a combination of the (E) component and the (F) component, it is preferable to use an aromatic tertiary amine as the (E) component and dibenzoyl peroxide as the (F) component, since this leads to superior curability of the resin composition.
The content of the (E) component in the resin composition is preferably 0.1 to 10 parts by mass, more preferably 0.3 to 8 parts by mass, and even more preferably 0.5 to 6 parts by mass, relative to 100 parts by mass of the total of the (A), (B), (C) and (D) components. The higher the content of the (E) component in the resin composition, the more improved the curability of the resin composition. The lower the content of the (E) component in the resin composition, the more improved the tensile strength of the cured product.
The amount of component (F) added to the resin composition immediately before curing is preferably 0.1 to 10 parts by mass, more preferably 0.3 to 8 parts by mass, and even more preferably 0.5 to 6 parts by mass, relative to 100 parts by mass of the total of components (A), (B), (C), and (D). The more the amount of component (F) added to the resin composition, the more the curability of the resin composition can be improved. The less the amount of component (F) added to the resin composition, the more the tensile strength of the cured product can be improved.

[Other radically polymerizable monomers]
The resin composition of this embodiment may contain radical polymerizable substances other than the components (A), (B), (C) and (D) (hereinafter referred to as "other polymerizable components") within a range that does not impair the effects of the present invention. When the other polymerizable components are contained, it may be easier to adjust the viscosity of the resin composition and the hardness of the cured product.
Examples of other polymerizable components include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, i-propyl (meth)acrylate, n-butyl (meth)acrylate, i-butyl (meth)acrylate, t-butyl (meth)acrylate, heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, n-nonyl (meth)acrylate, isononyl (meth)acrylate, decyl (meth)acrylate, lauryl (meth)acrylate, tridecyl (meth)acrylate, and stearyl (meth). ) acrylate and other alkyl (meth)acrylates; alkoxyalkyl (meth)acrylates such as methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate, and butoxyethyl (meth)acrylate; hydroxyl group-containing (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate; (meth)acrylic acid; polycaprolactone-modified (meth)acrylic acid esters such as ω-carboxy-polycaprolactone mono(meth)acrylate; 2-(meth)acryloyloxyethyl succinate monoester, 2-(meth) (meth)acrylates having a carboxy group, such as (meth)acryloyloxyalkyl dicarboxylic acid monoesters, such as acryloyloxyethyl hexahydrophthalic acid monoester, 2-(meth)acryloyloxyethyl phthalic acid monoester, 2-(meth)acryloyloxyethyl-2-hydroxyethyl-phthalic acid monoester, and 2-(meth)acryloyloxyethyl-2-hydroxypropyl-phthalic acid monoester; alkylene glycol-modified (meth)acrylates, such as 2-ethylhexyl diethylene glycol (meth)acrylate; polymerizable (meth)acrylates, such as 3-(meth)acryloxypropyl trimethoxysilane; ) Alkoxysilanes having an acryloyl group; phosphate polymerizable monomers such as 2-methacryloyloxyethyl acid phosphate and reaction products of 6-hexanolide addition polymers of 2-hydroxyethyl (meth)acrylate with phosphoric anhydride; (meth)acrylamide polymerizable monomers such as (meth)acrylamide, N-methylol (meth)acrylamide, and N,N-dimethylacrylamide; monofunctional (meth)acrylates other than component (A); aromatic vinyl monomers such as styrene and α-methylstyrene; cyanide vinyl monomers such as acrylonitrile; and vinyl ester monomers such as vinyl acetate.
The other polymerizable components may be used alone or in combination of two or more kinds.
The content of the other polymerizable components in the resin composition of this embodiment is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and even more preferably 10 parts by mass or less, based on the total of 100 parts by mass of the (A) component, the (B) component, the (C) component and the (D) component. As mentioned above, if the other polymerizable components are included, it may be easier to adjust the viscosity of the resin composition and the hardness of the cured product. The smaller the content of the other polymerizable components, the more the odor of the resin composition tends to be reduced.

[Other ingredients]
The resin composition of this embodiment may contain components other than the (A), (B), (C), and (D) components and other polymerizable components (hereinafter referred to as “other components”) as long as the effects of the present invention are not impaired.
Examples of other components include various additives such as paraffin wax, rubber, antioxidants, plasticizers, ultraviolet absorbers, thixotropic agents, antifoaming agents, polymerization inhibitors, silane coupling agents, and formalin catcher agents; and radical polymerization initiators such as thermal polymerization initiators and photopolymerization initiators.
The other components may be used alone or in combination of two or more.
Specific examples of other components will be described below.

Since the curing of the resin surface of the resin composition may be inhibited by oxygen in the air, paraffin wax may be blended into the resin composition to suppress the inhibition of curing. The melting point of the paraffin wax is preferably 40 to 80°C. The higher the melting point of the paraffin wax, the more sufficient the air barrier effect can be obtained, and the surface curing property of the resin composition can be improved. The lower the melting point of the paraffin wax, the better the solubility in the resin composition when preparing the resin composition.
Specific examples of paraffin waxes include "Paraffin 115" (product name, manufactured by Nippon Seiro Co., Ltd., melting point 47°C, hereinafter referred to as "P-115"), "Paraffin 130" (product name, manufactured by Nippon Seiro Co., Ltd., melting point 55°C, hereinafter referred to as "P-130"), and "Paraffin 150" (product name, manufactured by Nippon Seiro Co., Ltd., melting point 66°C, hereinafter referred to as "P-150").
It is preferable to use two or more kinds of paraffin waxes having different melting points in combination, because they can obtain a sufficient air barrier effect even when the temperature changes, and can maintain good surface curing properties of the resin composition. When using two or more kinds of paraffin waxes having different melting points in combination, it is preferable to use waxes having a melting point difference of about 5°C to 20°C.
As the paraffin wax, a wax dispersed in an organic solvent may be used in order to improve surface curing properties. When the paraffin wax is dispersed in an organic solvent and the dispersed wax is microparticulated to have a particle size of 0.1 to 50 μm, the air blocking effect is more easily exhibited. Paraffin wax dispersed in an organic solvent is commercially available, and examples thereof include "BYK-S780" (product name, manufactured by BYK Japan, petroleum naphtha dispersion of 10% by mass of paraffin wax, hereinafter referred to as "S780"). A commercially available product of paraffin wax dispersed in an organic solvent may be blended as it is.

The resin composition of this embodiment may contain a rubber component to improve the strength of the cured product. Examples of rubber components include (meth)acrylic acid ester-butadiene copolymers, (meth)acrylic acid ester-butadiene-styrene copolymers, polybutadiene rubber, chloroprene rubber, and acrylonitrile butadiene rubber.

The resin composition of this embodiment may contain an antioxidant to prevent oxidative deterioration of the cured product. Examples of the antioxidant include phenol-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants.
Specific examples of the antioxidant are given below.
Phenol-based antioxidants: n-octadecyl-3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate, tetrakis-[methylene-3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate]methane, triethylene glycol bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], and the like.
Phosphorus-based antioxidants: triphenyl phosphite, tris-isodecyl phosphite, tris-tridecyl phosphite, tris(2,4-di-t-butylphenyl) phosphite, and the like.
Sulfur-based antioxidants: dihexyl sulfide, dilauryl-3,3'-thiodipropionate, ditridecyl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, distereyl-3,3'-thiodipropionate, pentaerythritol tetrakis (β-laurylthiopropionate), and the like.

A plasticizer may be blended into the resin composition of this embodiment to adjust the hardness of the cured product. Examples of plasticizers include phthalates such as dibutyl phthalate, di-2-ethylhexyl phthalate, and diisodecyl phthalate; adipic esters such as di-2-ethylhexyl adipate and octyl adipate; sebacic esters such as dibutyl sebacate and di-2-ethylhexyl sebacate; azelaic esters such as di-2-ethylhexyl azelate and octyl azelate; and dibasic fatty acid esters; and paraffins such as chlorinated paraffin.

The resin composition of this embodiment may contain an ultraviolet absorber to suppress photodegradation of the cured product. Examples of ultraviolet absorbers include derivatives of 2-hydroxybenzophenone such as 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-octyloxybenzophenone, 2-hydroxy-4-decyloxybenzophenone, 2-hydroxy-4,4'-dimethoxybenzophenone, and 2-hydroxy-4,4'-dibutoxybenzophenone, or 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-ditertiarybutylphenyl)benzotriazole, or halides thereof, or phenyl salicylate, p-tertiarybutylphenyl salicylate, etc.

The resin composition of this embodiment may contain a thixotropic agent to suppress settling of aggregates and pigments that may be added when the composition is made into a paint. Examples of thixotropic agents include organic thixotropic agents such as urethane urea compounds, fatty acid amides, organic bentonite, oxidized polyethylene wax, and organically modified sepiolite, and inorganic thixotropic agents such as fine silica particles.

The resin composition of this embodiment may contain a defoaming agent to remove bubbles. Examples of the defoaming agent include an acrylic defoaming agent obtained by dissolving a special acrylic polymer in a solvent, and a vinyl defoaming agent obtained by dissolving a special vinyl polymer in a solvent.
Specific examples of the defoaming agent include the Disparlon series manufactured by Kusumoto Chemical Industries, Ltd. (product names: OX-880EF, OX-881, OX-883, OX-77EF, OX-710, OX-8040, 1922, 1927, 1950, P-410EF, P-420, P-425, PD-7, 1970, 230, 230HF, 230EF, LF-1980, LF-1982, LF-1983, LF-1984, and LF-1985, etc.) and BYK Japan's "BYK-052" and "BYK-1752".

The resin composition of this embodiment may be blended with a polymerization inhibitor to prevent polymerization of the resin composition before use and improve storage stability. Examples of polymerization inhibitors include hydroquinone, 2-methylhydroquinone, hydroquinone monomethyl ether, and 2-6-di-t-butyl-4-methylphenol.

When the resin composition of this embodiment is used as a paint, a silane coupling agent may be added to improve adhesion to aggregates and pigments that may be added to the paint. Examples of silane coupling agents include vinyltrichlorosilane, vinyltris(β-methoxyethoxy)silane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane other than γ-methacryloxypropyltrimethoxysilane, γ-glucidoxypropyltrimethoxysilane, and γ-mercaptopropyltrimethoxysilane.

In the resin composition of this embodiment, aldehyde may be generated during curing. In order to suppress the generation of such aldehyde, a formalin catcher agent may be blended into the resin composition. Examples of formalin catcher agents include amide compounds and hydrazide compounds. Specific examples of formalin catcher agents include the Riken Resin series manufactured by Miki Riken Kogyo Co., Ltd. (product names: C-40, FC-460, FC-480, FC-478T, FC-510PM, FC-8G, C-70, FCS-20, FCS-24, FCS-42, and FC-1000, etc.), and "ADH", "SDH", "DDH", "IDH", and "SAH" manufactured by Otsuka Chemical Co., Ltd.

In order to improve the curability of the resin composition of this embodiment, a thermal polymerization initiator may be blended. Examples of the thermal polymerization initiator include organic peroxides other than the component (F).
Examples of organic peroxides other than component (F) include azo compounds such as 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 1,1'-azobis-1-cyclohexanecarbonitrile, dimethyl-2,2'-azobisisobutyrate, 4,4'-azobis-4-cyanovaleric acid, and 2,2'-azobis-(2-amidinopropane)dihydrochloride.

In order to improve the curability of the resin composition of this embodiment, a photopolymerization initiator may be blended in. Examples of the photopolymerization initiator include benzophenone type compounds, anthraquinone type compounds, alkylphenone type compounds, thioxanthone type compounds, acylphosphine oxide type compounds, and phenyl glyoxylate type compounds.
Specific examples of the photopolymerization initiator are shown below.
Benzophenone type compounds: benzophenone, 4-methylbenzophenone, 2,4,6-trimethylbenzophenone, methyl orthobenzoylbenzoate, 4-phenylbenzophenone, and the like.
Anthraquinone type compounds: t-butylanthraquinone, 2-ethylanthraquinone, etc.
Alkylphenone type compounds: 2-hydroxy-2-methyl-1-phenylpropan-1-one, oligo{2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone}, benzyl dimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, benzoin methyl ether, 2-methyl-[4-(methylthio)phenyl]-2-morpholino-1-propanone, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methylpropan-1-one, and the like.
Thioxanthone type compounds: 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, diethylthioxanthone, isopropylthioxanthone, etc.
Acylphosphine oxide compounds: 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, and the like.
Phenylglyoxylate type compounds: phenylglyoxylic acid methyl ester, etc.

The content of the other components in the resin composition of this embodiment is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and even more preferably 10 parts by mass or less, per 100 parts by mass of the total amount of components (A), (B), (C), and (D).

[Method of producing resin composition]
The method for producing the resin composition of this embodiment is not particularly limited, but the following production method is preferred.
In a reaction vessel, in the first stage reaction, at least one of methyl methacrylate [component (b1)] and other acrylic monomers [component (b1)] is suspension polymerized with (meth)acrylic acid [component (b2)] to obtain a precursor copolymer (B') having a carboxy group.
In the second stage reaction, the obtained precursor copolymer (B') is added to the component (A) to form a solution. Glycidyl (meth)acrylate [component (b3)] is added to the solution, and the carboxy group of the precursor copolymer (B') reacts with the glycidyl group of the glycidyl (meth)acrylate to form an ester. This causes the glycidyl (meth)acrylate to be added to the precursor copolymer (B') to obtain the component (B) having a polymerizable double bond.
Next, the components (A), (B), (C), (D) and (E), and, if necessary, other polymerizable components and other components, are mixed to obtain the resin composition of this embodiment.
When mixing the components (A), (B), (C), (D) and (E), it is preferable to stir the components at room temperature or under heating at about 40 to 100° C. for 1 to 120 minutes.

[Viscosity of resin composition]
The viscosity of the resin composition is preferably in the range of 1 to 3,000 mPa·s, more preferably 1 to 2000 mPa·s, even more preferably 1 to 1500 mPa·s, and particularly preferably 100 to 1000 mPa·s, as measured at 23° C. using a Brookfield viscometer at a rotation speed of 60 rpm. If the viscosity of the resin composition is within the above range, the workability in coating is good.

[Action and Effect]
The resin composition of this embodiment contains both the (C) and (D) components, which are polyfunctional acrylates, in addition to the (A) component, which is a monofunctional (meth)acrylate having a cyclic structure, and the (B) component, which is an acrylic polymer. By containing both the (C) and (D) components, the resin composition can sufficiently cure the cured product, thereby improving both impact resistance and contamination resistance.
The resin composition of this embodiment containing the components (A), (B), (C) and (D) has little odor.

<Paint>
One embodiment of the coating material of the present invention contains the resin composition. The resin composition is suitable for coating materials because it can give a cured product having excellent hardness and impact resistance.
Examples of paints include road paints (e.g., anti-slip paints, drainage paints, heat-shielding paints, road marking paints, and paints for waterproofing decks), civil engineering and construction paints (e.g., wall paints, floor paints, roof paints, bridge paints, plant paints, steel structure paints, and concrete paints), furniture paints, decorative paints, electronic device paints, mobile device paints, home appliance paints, waterproof paints, automobile paints, motorcycle paints, heavy machinery paints, railway vehicle paints, and marine paints.

In the paint of this embodiment, aggregate may be blended. Examples of aggregate include sand, silica sand, river sand, kansui stone, emery, marble, calcium carbonate, kaolin, bentonite, mica, talc, silicon carbide powder, silicon nitride powder, boron nitride powder, alumina, slag, glass powder, ceramic aggregate, pottery waste, colored aggregate, hollow particles, etc. One type of aggregate may be used alone, or two or more types may be used in combination.
In the paint of this embodiment, a pigment may be blended to exhibit the effects of coloring, heat insulation, and heat dissipation. Examples of the pigment include organic pigments and inorganic pigments. Examples of the organic pigment include azo pigments and phthalocyanine pigments. Examples of the inorganic pigment include ceramic pigments, iron oxide, and titanium oxide. One type of pigment may be used alone, or two or more types may be used in combination.

<Cured Product>
One embodiment of the cured product of the present invention is obtained by curing the resin composition or the coating material.
The method for forming the cured product of this embodiment is not particularly limited, and examples thereof include a method of mixing the resin composition with the (F) component (Method 1), and a method of mixing the resin composition with a resin liquid in which the (F) component is dissolved (but does not contain the (E) component) (Method 2). When applying by hand, either Method 1 or Method 2 may be used. When applying by a two-liquid mixed spray, Method 2 is preferred because the blending ratio of the two agents is more likely to be stable.
When forming the cured product of this embodiment, the resin composition or the coating material may be allowed to stand after mixing with the (F) component. The ambient temperature during standing is not particularly limited, but is preferably -20 to 50°C, more preferably -10 to 45°C, and even more preferably 0 to 40°C, in terms of obtaining suitable curability. The standing time may be appropriately selected depending on the ambient temperature, the amount of the (E) component, and the amount of the (F) component. For example, when the standing temperature is -20 to 50°C, the curing reaction is almost completed if the standing time is in the range of 0.5 to 48 hours.

<Coating material>
One embodiment of the coating material of the present invention comprises a cured product of the resin composition.
The covering material of this embodiment is preferably used as a covering material for civil engineering and construction, and more preferably used as a covering material for construction surfaces such as floors, walls, and road pavement.
Examples of uses of the coating material of this embodiment include: a coating layer formed directly on the application surface; at least one of the layers when two layers, a primer layer and a topcoat layer, are formed on the application surface; and at least one of the layers when three layers, a primer layer, an intermediate layer and a topcoat layer, are formed on the application surface.
In particular, the coating material of this embodiment has excellent stain resistance and impact resistance, and can be suitably used as a topcoat layer and an undercoat layer. In anti-slip road pavement, it is preferable to provide a topcoat layer made of the coating material of this embodiment formed by applying and curing the resin composition of this embodiment on an undercoat layer or an intermediate coat layer formed by applying a mortar composition containing aggregate. Other layers may be provided between the undercoat layer and the intermediate coat layer, and between the intermediate coat layer and the topcoat layer.
The coating material of this embodiment is formed by applying the resin composition or the paint to a surface to be coated. Examples of a method for applying the resin composition include known coating methods using a roller, a metal trowel, a brush, a flexible broom, a coating machine (such as a spray coating machine), and the like.

<Other uses>
The resin composition of this embodiment can also be suitably used for other applications such as a casting material, a binder material, an adhesive, a repair material, and a joint material.
Specific examples of molded articles produced when the resin composition of this embodiment is used as a casting material include films, sheets, lenses, optical waveguides, sealing materials, etc. The molded articles are used, for example, in light-emitting diode modules, mobile phones, smartphones, tablet terminals, personal computers, cameras, organic electroluminescence (organic EL) devices, flat panel displays, touch panels, electronic paper, photodiodes, phototransistors, solar cells, projectors, etc. The molded articles can also be used as optical components.
Examples of the use of the resin composition of this embodiment as a binder include binders for artificial marble, fiber-reinforced plastics, and braille tiles.
Specific examples of the resin composition of this embodiment when used as an adhesive include, for example, an adhesive for glass, an adhesive for resin, and an adhesive for metal, and it can also be used as a second-generation acrylic adhesive (SGA).
Specific examples of the resin composition of this embodiment when used as a repair material include a concrete repair material and a road repair material.
Specific examples of the resin composition of this embodiment when used as a joint material include a joint material for tiles, a joint material for stones, a joint material for concrete, and a joint material for asphalt.

The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.
In the following examples, all "parts" mean "parts by mass", and all "%" means "% by mass" except for the degree of saponification.
The glass transition temperature (hereinafter referred to as "T _g ") of the polymer is a value measured using a DSC (EXSTAR6000 DSC6200, manufactured by Seiko Instruments Inc.).
The _Mw of the polymer was determined by dissolving a resin sample in tetrahydrofuran, measuring the molecular weight using a GPC apparatus (HLC-8320, manufactured by Tosoh Corporation), and converting the measured molecular weight into polystyrene equivalent.

[Production Example 1: Production of composition S-1 containing component (A) and component (B)]
First, the first stage reaction was carried out. That is, 135 parts of deionized water and 0.4 parts of polyvinyl alcohol (saponification degree 80 mol%, polymerization degree 1,700) as a dispersant were added to a polymerization apparatus equipped with a stirrer, a cooling tube, and a thermometer, and the mixture was stirred to completely dissolve the polyvinyl alcohol. Stirring was stopped once, and 4 parts of methacrylic acid (hereinafter referred to as "MAA"), 96 parts of methyl methacrylate (hereinafter referred to as "MMA"), 0.2 parts of 2,2'-azobis-2-methylbutyronitrile (hereinafter referred to as "AMBN") as a polymerization initiator, 0.8 parts of n-dodecyl mercaptan (hereinafter referred to as "n-DM") as a chain transfer agent, and 0.1 parts of sodium carbonate as an electrolyte were added, and the mixture was stirred again. The temperature inside the polymerization apparatus was raised to 75°C and reacted for 2.5 hours, and then the temperature was raised to 98°C, and the temperature was maintained for 1.5 hours to terminate the reaction. After cooling the inside of the polymerization apparatus to 40°C, the obtained aqueous suspension was filtered through a nylon filter cloth with a mesh size of 45 μm. The filtrate recovered by filtration was washed with deionized water, dehydrated, and then dried at 40°C for 16 hours to obtain a granular methacrylic polymer (precursor copolymer (B')). The obtained granular acrylic polymer had a _Tg of 100°C and a _Mw of 40,000. The _Tg and _Mw of the (B) component obtained in the second stage described below are the same as _those of the precursor _copolymer (B').
Next, the second stage reaction was carried out. That is, 6.6 parts of glycidyl methacrylate (hereinafter referred to as "GMA"), 1.5 parts of tetrabutylammonium bromide as an esterification catalyst, 0.1 parts of 2,6-di-t-butyl-4-methylphenol (hereinafter referred to as "BHT") as a polymerization inhibitor, and 200.9 parts of tetrahydrofurfuryl methacrylate (hereinafter referred to as "THFMA") were added to a polymerization apparatus equipped with a stirrer, a cooling tube, and a thermometer. While stirring the inside of the polymerization apparatus, 100 parts of the granular methacrylic polymer (precursor copolymer) obtained above were gradually added to the polymerization apparatus. After the entire amount of the granular methacrylic polymer was added to the polymerization apparatus, the temperature inside the polymerization apparatus was raised to 90 ° C. and maintained at that temperature for 2 hours. The molar ratio of GMA used in the second stage reaction was 1.0/1.0 relative to 1 mole of MAA used in the first stage reaction.
This resulted in a composition S-1 (hereinafter abbreviated as "S-1") containing component (B) having a polymerizable double bond and an acid value of 0.3 mgKOH/g and THFMA as component (A).

[Production Example 2: Production of composition S-2 containing component (A) and component (B)]
A granular vinyl polymer (precursor copolymer (B')) was obtained in the same manner as in Production Example 1, except that in the first-stage reaction of Production Example 1, the amount of MMA used was changed from 96 parts to 60 parts, and 36 parts of n-butyl methacrylate (hereinafter referred to as "n-BMA") was added to the polymerization reactor together with 60 parts of MMA and 4 parts of MAA. The _Mw of the obtained granular methacrylic polymer was 41,500.
The resulting granular methacrylic polymer was used to carry out a second-stage reaction in the same manner as in Production Example 1. This resulted in a composition S-2 (hereinafter abbreviated as "S-2") containing component (B) having a polymerizable double bond and an acid value of 0.3 mgKOH/g and component (A) THFMA.

[Production Example 3: Production of composition S-3 containing component (A) and component (B)]
In the second-stage reaction of Production Example 1, THFMA as component (A) was changed to benzyl methacrylate (hereinafter referred to as "BZMA"). Otherwise, the same procedure as in Production Example 1 was followed to obtain composition S-3 containing component (B) having a polymerizable double bond and an acid value of 0.3 mgKOH/g, and BZMA as component (A).

[Production Example 4: Production of composition S-4 containing component (A) and component (B)]
In the second-stage reaction of Production Example 1, THFMA as component (A) was changed to dicyclopentenyloxyethyl methacrylate (hereinafter referred to as "FA-512M"). Otherwise, the same procedure as in Production Example 1 was followed to obtain composition S-4 containing component (B) having a polymerizable double bond and an acid value of 0.3 mgKOH/g, and component (A) FA-512M.

[Production Example 5: Production of Polymer P-1 Having No Polymerizable Double Bond]
In the first stage reaction of Production Example 1, the amount of MMA used was changed from 96 parts to 80 parts, MAA was not used, and 20 parts of n-BMA was added to the polymerization apparatus together with 80 parts of MMA. Except for this, the same procedure as in Production Example 1 was repeated to obtain a granular methacrylic polymer P-1 (hereinafter referred to as "P-1") having no polymerizable double bond. P-1 had a _Tg of 82°C and a _Mw of 80,000.

[Example 1]
Using S-1 obtained in Production Example 1, a resin composition was prepared according to the formulation shown in Table 1.
Specifically, 50 parts of S-1 (32.5 parts of THFMA, 17.5 parts of component (B)), 30 parts of THFMA as component (A), 10 parts of ethylene glycol dimethacrylate as component (C), 10 parts of triethylene glycol dimethacrylate as component (D), 1 part of N,N-di(2-hydroxyethyl)-p-toluidine as component (E), 0.05 parts of BHT as a polymerization inhibitor, 0.4 parts of P-150, 0.6 parts of P-130, and 0.2 parts of P-115 as paraffin wax, 0.5 parts of a defoaming agent "Disparlon 230EF" (trade name, manufactured by Kusumoto Chemical Industries, Ltd.), and 3.3 parts of a formalin catcher agent "Riken Resin FCS-42" (trade name, manufactured by Miki Riken Kogyo Co., Ltd.) were added to a 1 L flask equipped with a stirrer, a thermometer, and a cooling tube.
Next, the inside of the flask was heated at 65° C. for 2 hours to dissolve each component. After that, the inside of the flask was cooled to 40° C. 3 parts of S780, which is a paraffin wax, was added to the cooled flask, and stirring was continued for 1 hour while maintaining the temperature at 40° C., to obtain a homogenized resin composition.

[Examples 2 to 15, 24 to 31]
Resin compositions were obtained in the same manner as in Example 1, except that the composition of each component was changed as shown in Table 1, Table 2, or Table 3. Although Tables 1, 2, and 3 do not show the amount of S-1 added to the 1 L flask, the total amount of THFMA contained in S-1 and component (B) contained in S-1 is the amount of S-1 added.

[Examples 16 and 20]
Resin compositions were obtained in the same manner as in Example 1, except that the compositions of the components were changed as shown in Tables 2 and 3. Although Tables 2 and 3 do not show the amount of S-2 added to the 1 L flask, the total amount of THFMA contained in S-2 and component (B) contained in S-2 is the amount of S-2 added.

[Examples 17, 18, and 21]
Resin compositions were obtained in the same manner as in Example 1, except that the compositions of the components were changed as shown in Tables 2 and 3. Although Tables 2 and 3 do not show the amount of S-3 added to the 1 L flask, the total amount of BZMA contained in S-3 and component (B) contained in S-3 is the amount of S-3 added.

[Example 22]
Resin compositions were obtained in the same manner as in Example 1, except that the composition of each component was changed as shown in Table 3. Although Table 3 does not show the amount of S-4 added to the 1 L flask, the amount of S-4 added is the sum of FA-512M contained in S-4 and component (B) contained in S-4.

[Examples 19 and 23]
Resin compositions were obtained in the same manner as in Example 1, except that the compositions of the components were changed as shown in Tables 2 and 3.

[Comparative Example 1]
As shown in Table 4, a resin composition was obtained in the same manner as in Example 1, except that the amount of EDMA, component (C), was changed to 20 parts by mass, and 3ED, component (D), was not added.

[Comparative Example 2]
As shown in Table 4, a resin composition was obtained in the same manner as in Example 1, except that EDMA, component (C), was not added, and instead 10 parts of 3ED and 10 parts of A-BPE-4, component (D), were added.

[Comparative Example 3]
As shown in Table 4, a resin composition was obtained in the same manner as in Example 6, except that the amount of BDMA as component (C) was changed to 20 parts by mass and 3ED as component (D) was not added.

[Comparative Example 4]
As shown in Table 4, a resin composition was obtained in the same manner as in Example 1, except that EDMA as component (C) was not added and 20 parts of 3ED as component (D) was added instead.

The abbreviations in the table mean the following substances.
-THFMA: Tetrahydrofurfuryl methacrylate.
BZMA: benzyl methacrylate.
- EDMA: Ethylene glycol dimethacrylate.
BDMA: 1,3-butylene glycol dimethacrylate.
3ED: Triethylene glycol dimethacrylate.
- MMA: Methyl methacrylate.
A-BPE-4: ethoxylated bisphenol A diacrylate (the total number of repeating ethoxy moieties in the molecule is about 4), "New Frontier BPE-4" (product name) manufactured by Daiichi Kogyo Seiyaku Co., Ltd.
PDP400N: Polypropylene glycol dimethacrylate, NOF Corporation's "Blenmer PDP400N" (product name).
FA-PTG9A: Polybutylene glycol diacrylate, "Fancryl FA-PTG9A" (product name) manufactured by Hitachi Chemical Co., Ltd.
PBOM: Polybutylene glycol dimethacrylate, "Acryester PBOM" (product name) manufactured by Mitsubishi Chemical Corporation.
Urethane acrylate: Aliphatic urethane acrylate, "EBECRYL230" (product name) manufactured by Daicel Allnex Corporation.
Polyester acrylate: "EBECRYL810" (product name) manufactured by Daicel Allnex Corporation.
Epoxy acrylate 1: "EBECRYL3500" (product name) manufactured by Daicel Allnex Corporation.
Epoxy acrylate 2: "EBECRYL3703" (product name) manufactured by Daicel Allnex Corporation.
PTEO: N,N-di(2-hydroxyethyl)-p-toluidine.
P150: Paraffin wax, "Paraffin Wax 150" (product name) manufactured by Nippon Seiro Co., Ltd., melting point 66°C.
P130: Paraffin wax, "Paraffin Wax 130" (product name) manufactured by Nippon Seiro Co., Ltd., melting point 55°C.
P115: Paraffin wax, "Paraffin Wax 115" (product name) manufactured by Nippon Seiro Co., Ltd., melting point 47°C.
S780: 10% paraffin wax petroleum naphtha dispersion, BYK-S780 (product name) manufactured by BYK Japan.
BHT: 2-6-di-t-butyl-4-methylphenol, "H-BHT" (trade name) manufactured by Honshu Chemical Co., Ltd.
- 230EF: Defoamer, "Disparlon 230EF" (product name) manufactured by Kusumoto Chemicals Co., Ltd.
FCS-42: Formalin catcher agent, "Riken Resin FCS-42" (product name) manufactured by Miki Riken Kogyo Co., Ltd.

<Evaluation>
The viscosity of each resin composition was measured and the odor was evaluated by the following method. In addition, an evaluation plate was prepared using each resin composition, and the stain resistance and impact resistance were evaluated. The measurement results and evaluation results are shown in Tables 1 to 4.

[Viscosity of resin composition]
The viscosity of the resin composition of each example was measured using a Brookfield viscometer at 23° C. and a rotation speed of 60 rpm.

[Odor]
A paint prepared by adding 3 parts of the curing agent "Niper NS" (trade name, NOF Corp., dibenzoyl peroxide suspension (purity 40%), hereinafter abbreviated as "Niper NS") to 100 parts of the resin composition of each example was applied to a 30 cm square slate board with a roller so that the coating amount was 0.5 kg/ ^m2 , and then cured. The odor during application was examined by three evaluators through a sensory test and evaluated according to the following criteria.
○: All three evaluators did not detect any odor.
×: One or more of the three evaluators felt an odor.

[Preparation of evaluation board]
A radical polymerization type acrylic resin primer "XD-9044" (product name, manufactured by Ryoko Co., Ltd.) was applied to one surface of a rectangular slate board measuring 70 mm x 170 mm using a roller so as to give a coating amount of 0.3 kg/ ^m2 , and then cured to form an undercoat layer.
Next, 100 parts of radical polymerization type acrylic resin base coat "XD-9353" (product name, manufactured by Ryoko Co., Ltd.) was mixed with 213 parts of aggregate "Acrytone Floor KC-1A" (product name, manufactured by Ryoko Co., Ltd.). Three parts of "Niper NS" were added to the resulting mixture to prepare an intermediate coating paint. The intermediate coating paint was applied to the surface of the undercoat layer to a thickness of 3 mm using a metal trowel and cured. The cured surface was polished with No. 400 sandpaper, and the shavings were removed to form an intermediate coating layer.
A coating film was formed on the surface of the intermediate layer by applying a coating material obtained by mixing 100 parts of the resin composition of each example with 3 parts of Nyper NS using a roller so as to achieve a coating amount of 0.3 kg/ ^m2 . The coating film was then cured sufficiently by curing for 7 days to form a topcoat layer. As a result, an evaluation panel was obtained in which the cured product of the resin composition of each example was used as the topcoat layer.

[Stain resistance]
Using the above evaluation board, a test was performed in accordance with JIS K-5600-5-4 (General test methods for paints, Mechanical properties of coating film, Scratch hardness (pencil method)), and the surface of the topcoat layer, which was the cured product of the resin composition of each example, was visually observed and evaluated according to the following evaluation criteria.
A: When the surface of the topcoat layer was scratched with a pencil having a hardness of 2H, no scratches were left.
B: When the surface of the topcoat layer was scratched with a pencil having a hardness of 2H or a pencil having a hardness softer than 2H, scratches were observed.
The more difficult the cured product is to scratch, the better its stain resistance.

[Impact resistance]
Using the above evaluation plates, tests were carried out in accordance with JIS K-5600-5-3 (general coating test methods, mechanical properties of coating film, weight drop resistance), and the surface of the topcoat layer, which was the cured product of the resin composition of each example, was visually observed and evaluated according to the following evaluation criteria. In the tests, a DuPont impact tester (manufactured by Toyo Seiki, product name H-50) was used. The DuPont impact tester was equipped with a striking die with a radius of 1/16 inch for striking the evaluation plate. The weight of the weight to be dropped onto the striking die was set to 300 g, and the falling height of the weight was set to 200 mm.
A: No cracks were observed in the topcoat layer.
B: Cracking of the topcoat layer was observed.

The resin compositions of each Example, which contained all of the (A), (B), (C) and (D) components, all had a suppressed odor. The resin compositions of each Example also had a viscosity suitable for coating. The cured products formed from the resin compositions of each Example had excellent stain resistance and impact resistance.
Comparing Example 10, in which the component (B) contains an acrylic polymer having a polymerizable double bond, with Example 23, in which the component (B) contains an acrylic polymer not having a polymerizable double bond, it is found that Example 10, in which the component (B) contains an acrylic polymer having a polymerizable double bond, has a higher surface hardness and is more resistant to contamination.
The resin compositions of Comparative Examples 1 and 3, which contained the components (A), (B) and (C) but did not contain the component (D), had low impact resistance in the cured products.
The resin compositions of Comparative Examples 2 and 4, which contained the components (A), (B) and (D) but did not contain the component (C), gave cured products with low stain resistance.

Claims (6)

A monofunctional (meth)acrylate having a cyclic structure (A),
(B) a (meth)acrylic polymer containing 20% by mass or more of a (meth)acrylic monomer unit;
a polyfunctional (meth)acrylate (C) comprising at least one of a difunctional (meth)acrylate represented by the following chemical formula (1) and a polyfunctional (meth)acrylate having a functionality of 3 or more and an acrylic equivalent of 170 or less;
(D) a polyfunctional (meth)acrylate other than the component (C);
and a reducing agent (E),
An acrylic curable resin composition comprising:
The (meth)acrylic polymer (B) has a polymerizable double bond,
The acrylic curable resin composition for a top coat layer is prepared by coating a mortar composition containing aggregate on an undercoat layer or intermediate coat layer formed by coating a coating film made of a cured product of the acrylic curable resin composition, the surface hardness of which is 2H or more when tested in accordance with JIS K-5600-5-4 (general test methods for paints, mechanical properties of coating films, scratch hardness (pencil method)).
CH ₂ ═C(R ¹ )COO—(R ² —O—) _n —OC(R ¹ )C═CH ₂ ... (1)
(In chemical formula (1), R ¹ is H or CH ₃ , R ² is an alkylene or hydroxyalkylene having 1 to 12 carbon atoms, and n is 1 or 2.) With respect to 100% by mass of the total of the components (A), (B), (C) and (D),
30 to 80% by mass of component (A),
5 to 30 mass% of component (B),
1 to 30 mass% of component (C),
Contains 1 to 30 mass% of component (D),
Relative to a total of 100 parts by mass of the components (A), (B), (C) and (D),
The acrylic curable resin composition according to claim 1, comprising 0.1 to 10 parts by mass of the component (E). The acrylic curable resin composition according to claim 1 or 2, wherein the component (A) is a monofunctional (meth)acrylate having at least one cyclic structure selected from the group consisting of a furan ring, a hydrofuran ring, a pyran ring, a hydropyran ring, an aromatic ring, and an alicyclic structure. A coating material containing the acrylic curable resin composition according to any one of claims 1 to 3. A cured product obtained by curing the acrylic curable resin composition according to any one of claims 1 to 3 or the coating material according to claim 4. A coating material for civil engineering and construction comprising the cured product according to claim 5.