JP2018131622A - Curable resin composition, and cured product thereof, and coating - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable resin composition that can be cured in a short time and gives a cured product having excellent adhesion to asphalt, hardness, and tensile strength.SOLUTION: A curable resin composition contains a monofunctional (meth) acrylate (A), a tri- or higher functional urethane (meth) acrylate (B), a (meth) acrylic polymer (C), a reductant (D), and a curing agent (E).SELECTED DRAWING: None

Description

  The present invention relates to a curable resin composition, a cured product thereof, and a paint.

  Room temperature curable (meth) acrylic resin compositions using benzoyl peroxide as a curing agent and tertiary amine as a curing accelerator are used to form various paints and adhesives for painted floors and road paving, artificial marble, etc. Widely used as a binder material for products.

  Various studies have been conducted to improve the workability of such a room temperature curable (meth) acrylic resin composition and the properties of the cured product.

  For example, in Patent Document 1, a radical polymerizable resin composition containing a radical polymerizable resin, a radical polymerizable monomer, and an acrylic polymer gives a coating film that has excellent surface drying properties and excellent tensile properties. Therefore, it is disclosed that it can be suitably used for flooring materials, paving materials, and the like.

Japanese Patent Laying-Open No. 2015-48459

  However, in the example of Patent Document 1, when bifunctional urethane methacrylate used as a radical polymerizable resin is used, the hardness of the cured product is lowered, so that the stain resistance of the coating film and the coating film There is a problem that durability becomes poor. In addition, since the curing time is long, when used as a paint for road pavement, asphalt is easily dissolved, resulting in poor adhesion.

  The present invention provides a curable resin composition capable of obtaining a cured product having a short curing time and excellent adhesion to asphalt, hardness, and tensile strength, a cured product thereof, and a coating containing the curable resin composition. The purpose is to do.

  According to one aspect of the present invention, a monofunctional (meth) acrylate (A), a tri- or higher functional urethane (meth) acrylate (B), a (meth) acrylic polymer (C), a reducing agent (D), A curable resin composition containing a curing agent (E) is provided.

  According to the other aspect of this invention, the coating material containing said curable resin composition is provided.

  According to the other aspect of this invention, the hardened | cured material of said curable resin composition is provided.

  According to the present invention, a curable resin composition capable of obtaining a cured product having a short curing time and excellent adhesion to asphalt, hardness, and tensile strength, a cured product thereof, and a coating containing the curable resin composition Can be provided.

In the present specification, “(meth) acryl” is a generic term for acrylic and methacrylic, “(meth) acrylate” is a generic term for acrylate and methacrylate, and “(meth) acryloyl group” means acryloyl group and methacryloyl. A general term for groups, CH ₂ ═C (R) —C (═O) — [R represents a hydrogen atom or a methyl group. ].

<Curable resin composition>
The curable resin composition according to the embodiment of the present invention includes a monofunctional (meth) acrylate (A), a tri- or higher functional urethane (meth) acrylate (B), a (meth) acrylic polymer (C), and a reducing agent. (D) contains a curing agent (E).

  In this specification, a monofunctional (meth) acrylate component is referred to as “component (A)”, a trifunctional or higher urethane (meth) acrylate component as “component (B)”, and a (meth) acrylic polymer component as “ “Component (C)”, the reducing agent component is referred to as “component (D)”, and the curing agent component is referred to as “component (E)”.

  This curable resin composition is 30 to 90% by mass of component (A) and 1 to 40% by mass of component (B) with respect to a total of 100% by mass of components (A), (B) and (C). The component (C) is contained in an amount of 0.1 to 30% by mass, and the component (D) is contained in an amount of 0.1 to 10% by mass with respect to a total of 100 parts by mass of the components (A), (B) and (C). It is preferable to contain 0.1-10 mass parts of a component and a component (E).

  This curable resin composition is useful as a component of a paint. For example, a road paint containing the curable resin composition and a road heat-shielding paint containing the curable resin composition can be provided.

[Component (A)]
The monofunctional (meth) acrylate as the component (A) is a (meth) acrylate compound having one (meth) acryloyl group in the molecular structure. A component (A) is a component for adjusting the viscosity of a curable resin composition to the value which is easy to work.

  Specific examples of component (A) include (meth) acrylic acid, 2- (meth) acryloyloxyethyl succinate, 2- (meth) acryloyloxyethyl maleate, 2- (meth) acryloyloxyethyl phthalate, hexa (Meth) acrylate having a carboxyl group such as 2- (meth) acryloyloxyethyl hydrophthalate; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4 -(Meth) acrylate having a hydroxyl group such as hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate; methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) Acrylate, i- Chill (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, heptyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, n- Alkyl (meth) acrylates such as nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate; cyclohexyl (meth) acrylate, di Cyclopentenyl (meth) acrylate, 2-dicyclopentenoxyethyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, adamantyl (meta Acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, phenoxypolypropylene glycol (meth) ) Acrylate, biphenyl (meth) acrylate, phenylphenoxyethyl (meth) acrylate, phenoxybenzyl (meth) acrylate, phenylbenzyl (meth) acrylate, naphthyl (meth) acrylate, (1-naphthyl) methyl (meth) acrylate, tetrahydrofur Furyl (meth) acrylate, glycidyl (meth) acrylate, (meth) acryloyl morph (Meth) acrylates having a cyclic structure such as oline; alkoxy (meth) acrylates such as methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate; 3- (meth) acryloxypropyltrimethoxy Examples include silane, 3- (meth) acryloxypropyltriethoxysilane, 2- (meth) acryloyloxyethyl acid phosphate, trifluoroethyl (meth) acrylate, and heptadecafluorodecyl (meth) acrylate. These components (A) may be used individually by 1 type, and may use 2 or more types together.

  A (meth) acrylate having a cyclic structure is preferred from the viewpoint of low odor and good tensile strength of the cured product. Among them, dicyclopentenyl (meth) acrylate, 2-diethyl is preferred from the viewpoint of tensile strength of the cured product. Cyclopentenoxyethyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, and tetrahydrofurfuryl (meth) acrylate are particularly preferable.

  The content of the component (A) in the curable resin composition is preferably 30 to 90% by mass, and preferably 40 to 85 when the total amount of the components (A), (B) and (C) is 100% by mass. % By mass is more preferable, and 50 to 80% by mass is more preferable. By setting it as 30 mass% or more, since the viscosity of curable resin composition becomes low level, workability | operativity improves. By setting it as 90 mass% or less, since content of a component (B) and a component (C) can be increased, hardening time can be shortened.

[Component (B)]
The trifunctional or higher functional urethane (meth) acrylate as the component (B) is a urethane (meth) acrylate compound having three or more (meth) acryloyl groups in the molecular structure. Component (B) is a component for improving the adhesion of the cured product to asphalt by shortening the curing time of the curable resin composition, and further improving the hardness and strength of the cured product.

  Although the manufacturing method of component (B) is not particularly limited, for example, a method of reacting a compound having three or more isocyanate groups in the molecular structure with a (meth) acrylate compound having one hydroxyl group in the molecular structure, Examples thereof include a method of reacting a compound having three or more hydroxyl groups in the molecular structure with a (meth) acrylate compound having one isocyanate group in the molecular structure.

  Specific examples of the component (B) include, for example, commercially available product names of “EXCRATE series” manufactured by Asia Kogyo Co., Ltd .: “RUA-003VE” (15 functional), “RUA-003LD” (15 functional), “RUA-” 065 "(10 functional)," RUA-066SP "(10 functional), RUA-077 (10 functional)," RUA-004MG "(9 functional)," RUA-071 "(6 functional)," RUA-076MG " ”(6 functional),“ RUA-064S-8 ”(5 functional),“ RX12-89 ”(5 functional),“ RUA-075 ”(5 functional),“ SUA-0009 ”(4 functional),“ RUA ” -049X "(trifunctional)," RUA-051 "(trifunctional)," RUA-048 "(trifunctional), etc., and the product name of" NK Oligo "series manufactured by Shin-Nakamura Chemical Co., Ltd .:" UA-31F " (Trifunctional , "UA-7100" (3 functional), "U-6LPA" (6 functional), "U-10PA" (10 functional), "U-10HA" (10 functional), "UA-33H" (9 functional) , “UA-53H” (15 functions), “UA-32P” (3 functions), “UA-1100H” (6 functions), and the like. These components (B) may be used individually by 1 type, and may use 2 or more types together.

  Since the tensile strength of the cured product is good, the number of functional groups in the component (B) is preferably 3 to 10.

  The content of the component (B) in the curable resin composition is preferably 1 to 40% by mass and more preferably 5 to 35% by mass when the total amount of the components (A) to (C) is 100% by mass. Preferably, 10 to 30% by mass is more preferable. By setting the content to 1% by mass or more, the curing time of the curable resin composition can be shortened. By setting it to 40% by mass or less, the hardness and tensile strength of the cured product can be improved.

[Component C]
The component (C) (meth) acrylic polymer is a polymer containing 20% by mass or more of (meth) acrylic monomer units in the composition, shortening the curing time of the curable resin composition, It is a component that improves the curability of the surface (air contact surface) of the curable resin composition. The (meth) acrylic monomer means a monomer having a (meth) acryloyl group. “Unit” means a repeating unit constituting a polymer.

  The (meth) acrylic monomer may be a monofunctional monomer or a polyfunctional monomer, but a monofunctional monomer is preferred from the viewpoint of solubility in the component (A) and the component (B).

  Specific examples of the monofunctional monomer include (meth) acrylic acid, 2- (meth) acryloyloxyethyl succinate, 2- (meth) acryloyloxyethyl maleate, 2- (meth) acryloyloxyethyl phthalate, hexahydro (Meth) acrylate having a carboxyl group such as 2- (meth) acryloyloxyethyl phthalate; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4- (Meth) acrylate having a hydroxyl group such as hydroxybutyl (meth) acrylate and 6-hydroxyhexyl (meth) acrylate; methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate , -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 -Alkyl (meth) acrylates such as nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate; cyclohexyl (meth) acrylate, Dicyclopentenyl (meth) acrylate, 2-dicyclopentenoxyethyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, adamantyl ( Acrylate), phenyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, phenoxypolypropylene 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) acrylo (Meth) acrylates having a cyclic structure such as ilmorpholine; alkoxy (meth) acrylates such as methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate; 3- (meth) acryloxypropyl Examples include trimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 2- (meth) acryloyloxyethyl acid phosphate, trifluoroethyl (meth) acrylate, and heptadecafluorodecyl (meth) acrylate.

  Specific examples of the polyfunctional monomer include ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, and 1,9-nonane. Polyalkylene glycol di (meth) acrylates such as alkylene glycol di (meth) acrylates such as diol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate and polybutylene glycol di (meth) acrylate , Neopentyl glycol di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, polycarbonate diol di (meth) acrylate, polyester diol di (meth) Bifunctional such as acrylate, EO-modified bisphenol A di (meth) acrylate, propoxylated bisphenol A di (meth) acrylate, 9,9-bis (4- (meth) acryloyloxyethoxyphenyl) fluorene, urethane di (meth) acrylate (Meth) acrylate; trifunctional (meth) acrylate such as trimethylolpropane tri (meth) acrylate, EO-modified isocyanuric acid tri (meth) acrylate, and ε-caprolactone-modified tris ((meth) acryloxyethyl) isocyanurate; Tetrafunctional (meth) acrylates such as methylolpropane tetra (meth) acrylate; pentafunctional (meth) acrylates such as dipentaerythritol penta (meth) acrylate; dipentaerythritol hexa (meth) acrylate And polyfunctional monomers such as hexafunctional (meth) acrylates.

  1 type or 2 types or more may be sufficient as the (meth) acrylic-type monomer unit contained in a component (C). Moreover, the component (C) may contain other monomer units other than the (meth) acrylic monomer unit. Other monomers may be any monomers that can be copolymerized with (meth) acrylic monomers, such as aromatic vinyl monomers such as styrene and α-methylstyrene; vinyl cyanide monomers such as acrylonitrile; vinyl acetate. And vinyl ester monomers such as In the component (C), the proportion of the (meth) acrylic monomer unit is 20% by mass or more, preferably 50% by mass or more, and more preferably 80% by mass or more. The upper limit of the ratio is not particularly limited, and may be 100% by mass.

  Preferred specific examples of the component (C) include polymethyl methacrylate, polyethyl methacrylate, polybutyl methacrylate, a copolymer composed of methyl methacrylate units and n-butyl methacrylate units, methyl methacrylate units and n-butyl acrylate units. And a copolymer. Among these, from the viewpoint of transparency of the cured product, polymethyl methacrylate, a copolymer composed of a methyl methacrylate unit and an n-butyl methacrylate unit, and a copolymer composed of a methyl methacrylate unit and an n-butyl acrylate unit are preferable.

  The mass average molecular weight of the component (C) is preferably 5,000 to 500,000, and more preferably 10,000 to 200,000. When the mass average molecular weight is 5,000 or more, the strength of the cured product is improved. When it is 500,000 or less, the viscosity of the curable resin composition is lowered, and thus workability is improved.

  The polymerization method for obtaining the component (C) is not particularly limited, and for example, the polymerization can be performed by a known method such as a solution polymerization method, a suspension polymerization method, an emulsion polymerization method, or a partial polymerization method. In the present invention, the suspension polymerization method is preferred because it is relatively easy to control the polymerization reaction and to separate the produced polymer.

  These components (C) may be used individually by 1 type, and may use 2 or more types together.

  The content of the component (C) in the curable resin composition is preferably 0.1 to 30% by mass when the total amount of the components (A), (B) and (C) is 100% by mass, and 0 5 to 25% by mass is more preferable, and 1 to 20% by mass is even more preferable. By setting the content to 0.1% by mass or more, the curing time of the curable resin composition can be shortened. By setting it as 30 mass% or less, since the viscosity of curable resin composition becomes low level, workability | operativity improves.

[Component (D) and Component (E)]
In the curable resin composition according to the embodiment of the present invention, a polymerization reaction proceeds by a radical generated from a redox polymerization initiator, and the composition is cured. A redox-type polymerization initiator is a polymerization initiator which used together the reducing agent which is a component (D), and the hardening | curing agent which is a component (E). Examples of the combination of the component (D) and the component (E) used for the redox polymerization initiator include the following (1) to (5).

(1) A combination of aromatic tertiary amines as component (D) and dibenzoyl peroxide as component (E).
Examples of aromatic tertiary amines include N, N-dimethyl-p-toluidine, N, N-diethylaniline; N, N-diethyl-p-toluidine; N- (2-hydroxyethyl) N-methyl- 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 (2-hydroxypropyl) -p-toluidine ethylene oxide adduct; N, N-di (2-hydroxyethyl) -p-toluidine or N, N-di (2-hydroxypropyl) -P-toluidine propylene oxide adduct and the like. These aromatic tertiary amines are not limited to the p (para) form, and may be an o (ortho) form or an m (meth) form.

(2) A combination of metal soaps as component (D) and dibenzoyl peroxide as component (E).
Specific examples of metal soaps include, for example, cobalt naphthenate, copper naphthenate, manganese naphthenate, cobalt 2-ethylhexanoate, nickel 2-ethylhexanoate, cobalt acetylacetonate, zinc acetylacetonate, aluminum acetylacetate Nate, iron acetylacetonate, vanadyl acetylacetonate, vanadium acetylacetonate and the like.

(3) A combination of metal soaps as component (D) and hydroperoxide as component (E).
Specific examples of metal soaps include those described above.
Specific examples of the hydroperoxide include, for example, cumene hydroperoxide, p-menthane hydroperoxide, diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, and t-butyl hydroperoxide. , T-hexyl hydroperoxide, t-amyl hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide and the like.

(4) A combination of the thiourea compound as component (D) and the hydroperoxide as component (E).
Specific examples of the hydroperoxide include those described above.
Specific examples of the thiourea compound include, for example, thiourea, ethylenethiourea, N, N′-dimethylthiourea, N, N′-diethylthiourea, N, N′-dipropylthiourea, N, N′-di-n- Examples thereof include butylthiourea, N, N′-dilaurylthiourea, N, N′-diphenylthiourea, trimethylthiourea, 1-acetyl-2-thiourea, 1-benzoyl-2-thiourea and the like.

(5) A combination of a thiourea compound as component (D) and a monocarbonate type peroxide as component (E).
Specific examples of the thiourea compound include those described above.
Specific examples of the monocarbonate type peroxide include, for example, t-hexyl peroxyisopropyl monocarbonate, t-butyl peroxyisopropyl monocarbonate, t-butyl peroxy 2-ethylhexyl monocarbonate, t-butyl peroxyallyl monocarbonate. Examples include carbonate and 1,6-bis (t-butylperoxycarbonyloxy) hexane.

  These component (D) and component (E) may be used individually by 1 type, respectively, and may use 2 or more types together.

  From the viewpoint of improving the adhesion to asphalt by shortening the curing time of the curable resin composition, an aromatic tertiary amine and a metal soap are used in combination as the component (D), and dibenzoyl is used as the component (E). It is particularly preferable to use peroxide. From the viewpoint of increasing the strength of the cured product, aromatic tertiary amines 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 are particularly preferred, and metal soaps include cobalt naphthenate, copper naphthenate, manganese naphthenate, cobalt octylate, vanadyl acetylacetonate. Is preferred.

  Content of (D) component and (E) component in curable resin composition is 0.1-10 mass parts with respect to 100 mass parts of total amounts of (A), (B), and (C) component, respectively. Is preferable, 0.3-8 mass parts is more preferable, and 0.5-6 mass parts is further more preferable. By setting it as 0.1 mass part or more, sclerosis | hardenability of curable resin composition can be made favorable. By setting it as 10 mass parts or less, the tensile strength of hardened | cured material can be made favorable.

[Other radical polymerizable monomers]
The curable resin composition by embodiment of this invention can contain another radically polymerizable monomer (F) as polymerizable monomers other than the said component (A) and component (B). By containing other radically polymerizable monomer (F), the viscosity, hardness or tensile strength may be further improved.

  Specific examples of the other radical polymerizable monomer (F) include, for example, aromatic vinyl monomers such as styrene and α-methylstyrene; vinyl cyanide monomers such as acrylonitrile; vinyl ester monomers such as vinyl acetate; Examples thereof include polyfunctional monomers other than (B).

Specific examples of the polyfunctional monomer other than the component (B) include bifunctional (meth) acrylates such as ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, 1, Alkylene glycol di (meth) acrylates such as 6-hexanediol di (meth) acrylate and 1,9-nonanediol di (meth) acrylate; polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polybutylene glycol Polyalkylene glycol di (meth) acrylate such as di (meth) acrylate; Neopentyl glycol di (meth) acrylate; Tricyclodecane dimethanol di (meth) acrylate; Polyester diol di (meth) acrylate; EO-modified bisphenol A di (meth) acrylate; propoxylated bisphenol A di (meth) acrylate; 9,9-bis (4- (meth) acryloyloxyethoxyphenyl) fluorene; Urethane di (meth) acrylate and the like,
Examples of the trifunctional (meth) acrylate include trimethylolpropane tri (meth) acrylate, EO-modified isocyanuric acid tri (meth) acrylate, and ε-caprolactone-modified tris ((meth) acryloxyethyl) isocyanurate.
Examples of the tetrafunctional (meth) acrylate include ditrimethylolpropane tetra (meth) acrylate,
Examples of pentafunctional (meth) acrylates include dipentaerythritol penta (meth) acrylate,
Examples of the hexafunctional (meth) acrylate include dipentaerythritol hexa (meth) acrylate.

These other radically polymerizable monomers (F) may be used individually by 1 type, and may use 2 or more types together.
Other radical polymerizable monomers (F) are composed of 1,9-nonanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, tricyclodecane dimethanol dimer from the viewpoint of hardness and tensile strength of the cured product. (Meth) acrylate, EO-modified bisphenol A di (meth) acrylate, and trimethylolpropane tri (meth) acrylate are preferred.

  The other radical polymerizable monomer (F) is preferably 35% by mass or less, more preferably 30% by mass or less, and further preferably 25% by mass or less in the total amount of 100% by mass of the curable resin composition. As described above, the viscosity, hardness, and tensile strength may be further adjusted when the curable resin composition contains other radical polymerizable monomer (F). When the content of the other radical polymerizable monomer (F) is 30% by mass or less in the total amount of 100% by mass of the curable resin composition, the viscosity of the curable resin composition, the hardness of the cured product, and the tensile strength. Can be further improved.

[Other ingredients]
If the curable resin composition by embodiment of this invention is in the range which does not impair the effect of this invention, other than the component (A)-(E) mentioned above and other radically polymerizable monomers (F) are mentioned. Component (G) may be included.

  As other components (G), for example, various additives such as paraffin wax, rubber, antioxidant, plasticizer, ultraviolet absorber, thixotropic agent, antifoaming agent, polymerization inhibitor, silane coupling agent, etc .; thermal polymerization Examples thereof include radical polymerization initiators such as initiators and photopolymerization initiators.

Paraffin wax may be added to the curable resin composition according to the embodiment of the present invention in order to suppress the inhibition of curing of the resin surface by oxygen. It is preferable to use two or more paraffin waxes having different melting points. The melting point of the paraffin wax is preferably 40 to 80 ° C. Specific examples of the paraffin wax include the following. Paraffin 115 (melting point described in catalog: 47 ° C, manufactured by Nippon Seiwa Co., Ltd.), paraffin 130 (melting point described in catalog: 55 ° C, manufactured by Nippon Seiwa Co., Ltd.), paraffin 150 (melting point described in catalog: 66 ° C, Nippon Seiwa) Etc.). If melting | fusing point is 40 degreeC or more, when hardening a resin composition, sufficient air blocking effect will be acquired and surface curability will become favorable. On the other hand, when the melting point is 80 ° C. or lower, the solubility of paraffin wax in the resin composition is improved when preparing the resin composition. Further, by using paraffin waxes having different melting points in combination, a sufficient air blocking action can be obtained even when the temperature is changed, and the surface curability is improved. When using together, it is preferable to use together that whose melting | fusing point difference is about 5 to 20 degreeC.
As the paraffin wax, a wax dispersed in an organic solvent may be used in terms of improving the surface curability. Since the wax is dispersed in the organic solvent and the particle diameter of the wax in the dispersed state is finely divided to 0.1 μm to 50 μm, the air blocking action is effectively expressed. For example, commercially available “BYK-S780 (trade name)” manufactured by Big Chemie Japan can be added to the paraffin wax in a dispersed state.

  In order to improve the strength of the cured product, rubber may be added to the curable resin composition according to the embodiment of the present invention. Specific examples of the rubber include the following. (Meth) acrylic acid ester-butadiene copolymer, (meth) acrylic acid ester / butadiene / styrene copolymer, polybutadiene rubber, chloroprene rubber, acrylonitrile butadiene rubber and the like.

  An antioxidant may be added to the curable resin composition according to the embodiment of the present invention in order to prevent oxidative degradation of the cured product. Specific examples of the antioxidant include the following. 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-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol bis [3- (3,5-di- t-butyl-4-hydroxyphenyl) propionate] and the like; triphenyl phosphite, trisisodecyl phosphite, tristridecyl phosphite, tris (2,4-di-t-butylphenyl) phos Phosphorous antioxidants such as phyto; dihexyl sulfide, dilauryl 3,3′-thiodipropionate, ditri Sulfur such as syl-3,3′-thiodipropionate, dimyristyl-3,3′-thiodipropionate, distereal-3,3′-thiodipropionate, pentaerythritol tetrakis (β-laurylthiopropionate) System antioxidants.

  In order to adjust the hardness of the cured product, a plasticizer may be added to the curable resin composition according to the embodiment of the present invention. Specific examples of the plasticizer include the following. Phthalate esters such as dibutyl phthalate, di-2-ethylhexyl phthalate, diisodecyl phthalate, adipates such as di-2-ethylhexyl adipate, octyl adipate, dibutyl sebacate, di-2-ethylhexyl sebacate, etc. Dibasic fatty acid esters such as sebacic acid esters, azelain esters such as di-2-ethylhexyl azelate and octyl azelate; paraffins such as chlorinated paraffin and the like.

  In order to suppress photodegradation of the cured product, an ultraviolet absorber may be added to the curable resin composition according to the embodiment of the present invention. Specific examples of the ultraviolet absorber include the following. 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-octyloxybenzophenone, 2-hydroxy-4-decyloxybenzophenone, 2-hydroxy-4,4′-dimethoxybenzophenone, 2-hydroxy-4,4′-dibutoxy 2-hydroxybenzophenone derivatives such as benzophenone; 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-ditertiarybutylphenyl) benzotriazole or these Halides; phenyl salicylate, p-tertiary butyl phenyl salicylate, hydroxyphenyl triazine-based ultraviolet absorbers, and the like.

  A thixotropic agent may be added to the curable resin composition according to the embodiment of the present invention in order to suppress sedimentation of aggregates and pigments to be blended when forming a paint. Specific examples of the thixotropic agent include an organic thixotropic agent such as urethane urea, fatty acid amide, organic bentonite, oxidized polyethylene wax, and organic modified sepiolite, and an inorganic thixotropic agent such as fine-particle silica.

  An antifoaming agent may be added to the curable resin composition according to the embodiment of the present invention in order to remove bubbles. Specific examples of the antifoaming agent include an acrylic antifoaming agent obtained by dissolving a special acrylic polymer in a solvent, and a vinyl antifoaming agent obtained by dissolving a special vinyl polymer in a solvent. Specific examples of the product name of the antifoaming agent include the following. Product name of Disparon series manufactured by Enomoto Kasei Co., Ltd .: 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, LF-1985, etc. and product names manufactured by BYK Japan Japan: BYK-052, BYK -1752, etc.

  In order to improve storage stability, a polymerization inhibitor may be added to the resin composition according to the embodiment of the present invention. Specific examples of the polymerization inhibitor include hydroquinone, 2-methylhydroquinone, hydroquinone monomethyl ether, 2-6-di-t-butyl-4-methylphenol, and the like.

  A silane coupling agent may be added to the curable resin composition according to the embodiment of the present invention in order to improve the adhesion to aggregates and pigments to be blended when forming a paint. Specific examples of the silane coupling agent include the following. 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 3- (glycidoxypropyl) trimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-aminopropyltriethoxy Silane etc.

  A thermal polymerization initiator may be added to the curable resin composition according to the embodiment of the present invention in order to improve curability. Specific examples of the thermal polymerization initiator include the following. Ketone peroxides such as methyl ethyl ketone peroxide; 1,1-di (t-hexylperoxy) -3,3,5-trimethylcyclohexane, 1,1-di (t-hexylperoxy) cyclohexane, 1,1-di Peroxyketals such as (t-butylperoxy) cyclohexane; Dialkyl peroxides such as dicumyl peroxide and di-t-butyl peroxide; Diacyl peroxides such as dilauroyl peroxide; Di (4-t-butylcyclohexyl) ) Peroxydicarbonates such as peroxydicarbonate and di (2-ethylhexyl) peroxydicarbonate; t-butylperoxy-2-ethylhexanoate, t-hexylperoxyisopropylmonocarbonate, t-butylperoxy Benzoate, , 1,3,3-tetramethylbutylperoxy-2-ethylhexanoate and other peroxides; 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, 2,2′-azobis- (2-amidinopropane) dihydrochloride and other azo compounds.

  In order to improve sclerosis | hardenability, you may add a photoinitiator to the curable resin composition by embodiment of this invention. Specific examples of the photopolymerization initiator include the following. Benzophenone type compounds such as benzophenone, 4-methylbenzophenone, 2,4,6-trimethylbenzophenone, methylorthobenzoylbenzoate, 4-phenylbenzophenone; anthraquinone type compounds such as t-butylanthraquinone and 2-ethylanthraquinone; 2-hydroxy 2-methyl-1-phenylpropan-1-one, oligo {2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone}, benzyldimethyl 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}- -Alkylphenone type compounds such as methylpropan-1-one; thioxanthone type compounds such as 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, diethylthioxanthone, isopropylthioxanthone; 2,4 , 6-trimethylbenzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, etc. Oxide type compounds; phenyl glyoxylate type compounds such as phenyl glyoxylic acid methyl ester.

  These other components (G) may be used individually by 1 type, and may use 2 or more types together.

  The content of the other component (G) is preferably 20% by mass or less, and preferably 15% by mass or less, in the total amount of 100% by mass of the curable resin composition, from the viewpoint of not impairing desired properties of the curable resin composition. More preferred is 10% by mass or less.

<Method for producing curable resin composition>
Although the manufacturing method of the curable resin composition by embodiment of this invention is not specifically limited, From a workability | operativity point, component (A)-(D) and other radically polymerizable monomers (F as needed) previously. ) And other components (G) are preferably mixed to prepare a resin composition. As a method of mixing the components (A) to (D), it is preferable to perform stirring and mixing over 1 to 120 minutes at room temperature or under heating at about 40 to 80 ° C. Component (E) is preferably stirred and mixed at room temperature immediately before curing the curable resin composition from the viewpoint of storage stability of the curable resin composition.

<Viscosity of resin composition>
The viscosity of the resin composition not containing the component (E) that is a curing agent is preferably such that the measured value at a rotational speed of 60 rpm using a B-type viscometer at 23 ° C. is in the range of 1 to 1,000 mPa · s. More preferably, it is 1-500 mPa * s, More preferably, it is 1-300 mPa * s. When the viscosity of the curable resin composition is within the above range, workability such as coating is improved.

<Curing time of curable resin composition>
The curing time of the curable resin composition measured under the following conditions is preferably 1 to 8 minutes, more preferably 1 to 7 minutes, and further preferably 1 to 6 minutes. When the curing time of the curable resin composition is within the above range, the adhesion of the cured product to asphalt becomes good.

  In the air at 23 ° C., the resin composition containing components other than the component (E) is blended and mixed with the component (E) to obtain a curable resin composition. Put up to 70 mm from the bottom into a 120 mm test tube. A thermocouple is placed in the curable resin composition in the test tube, and the test tube is left in water at 23 ° C. The temperature change of the curable resin composition after that is measured with a thermocouple. The time until the temperature of the curable resin composition is maximized is defined as the curing time, starting from the time when the component (E) is blended.

<Hardness of cured product>
The hardness of the cured product of the curable resin composition according to the embodiment of the present invention is a type D durometer according to JIS K6253, in which two 3 mm-thick evaluation sheet-like cured products prepared by the following method are stacked to a thickness of 6 mm. When the hardness at 23 ° C. is measured, it is preferably D30 to D95, more preferably D40 to D95, and even more preferably D50 to D95. By setting it as the above range, the stain resistance of the cured product is improved.

  Said evaluation sheet-like hardened | cured material is produced with the following method. Pour the vacuum defoamed curable resin composition into two glass plates coated with a release PET film on the surface in contact with the curable resin composition and a glass cell made of a vinyl chloride gasket, for 12 hours at 23 ° C. Curing with. After curing, the plate glass and the PET film are removed to obtain a sheet-like cured product for evaluation having a length of 250 mm, a width of 250 mm, and a thickness of 3 mm.

<Tensile strength of cured product>
The curable resin composition according to the embodiment of the present invention is obtained by punching out the dumbbell-shaped No. 1 described in JISK6251 from the above-described evaluation sheet-like cured product having a thickness of 3 mm, “distance between chucks: 50 mm, tensile speed: 20 mm. / Min. ”, The tensile strength when the tensile test is performed is preferably ² N / mm ² or more, more preferably 3 N / mm ² or more, and further preferably 4 N / mm ² or more. preferable. If the tensile strength of this evaluation method is 2 N / mm ² or more, the durability of the cured product becomes good, and defects such as cracks during actual use can be suppressed.

<Paint>
The curable resin composition according to the embodiment of the present invention can be suitably used as a resin for a coating because a cured product having excellent hardness and tensile strength is obtained.

  Specific examples of paints include, for example, anti-slip paints, drainage paints, thermal barrier paints, road marking paints, floor slab paints, road paints, wall paints, floor paints, and roof paints. , Paints for bridges, paints for plants, paints for iron structures, paints for civil engineering and construction such as paints for concrete, paints for furniture, paints for decorations, paints for electronic devices / mobiles, paints for home appliances, paints for waterproofing, automobiles Paints, motorcycle paints, heavy machinery paints, railway vehicle paints, marine paints, and the like.

  When using the curable resin composition by embodiment of this invention as a coating material, you may mix | blend and use an aggregate. Specific examples of aggregates include sand, dredged sand, river sand, cold water stone, emery, marble, calcium carbonate, kaolin, bentonite, mica, talc, silicon carbide powder, silicon nitride powder, boron nitride powder, alumina, slag, glass Examples thereof include powder, ceramic aggregate, ceramic scrap, colored aggregate, and hollow particles. In addition, a pigment may be blended in order to exhibit effects of coloring, heat shielding, and heat dissipation. Specific examples of the pigment include organic pigments such as azo pigments and phthalocyanine pigments; ceramic pigments, inorganic pigments such as iron oxide and titanium oxide, and the like.

<Road paint>
The road paint is a paint for imparting a function to the road pavement surface. When applying to the road, it is necessary to close the road, but since the curable resin composition according to the embodiment of the present invention has a short curing time, when a road paint containing this curable resin composition is used, Road closure time can be shortened. As the types of pavement, there are asphalt pavement, concrete pavement, etc., and the curable resin composition according to the embodiment of the present invention is particularly suitable as a paint for asphalt pavement because a cured product having excellent adhesion to asphalt is obtained. Can be used for

  Examples of road paints to which the curable resin composition according to embodiments of the present invention can be applied include anti-slip paints, drainage paints, thermal barrier paints, road marking paints, floor slab waterproofing paints, and the like. .

<Thermal barrier paint for road>
The thermal barrier paint for roads is a functional paint that highly reflects near-infrared light during solar radiation and suppresses temperature rise on the road surface. As the thermal barrier paint for roads, generally used is a room temperature curable resin blended with a light reflecting pigment or hollow particles. The curable resin composition according to the embodiment of the present invention can be applied to such a thermal barrier paint for roads.

  The light-reflecting pigment absorbs in the visible region and reflects in the near-infrared region, so that it absorbs less heat energy and can prevent the temperature of the coating from rising. Examples of the light reflecting pigment include a pigment having a solar reflectance of 12% or more in a region of 350 to 2100 nm defined by JISA5759 (sunlight shielding / film for preventing glass scattering). Here, the solar reflectance data is measured in a sufficiently concealed state, specifically, in a coating film having a concealment rate of about 1.0. Examples of the pigment having a solar reflectance of 12% or more that can be used as a light reflecting pigment include black or dark pigments such as black pigments; colored pigments such as yellow pigments, red pigments, blue pigments, and green pigments; And white pigments.

Specific examples of black or dark pigments such as azomethyazo-based black pigment of trade name: Chromofine Black A-1103 (manufactured by Dainichi Seika Kogyo Co., Ltd.), trade name: Dipiroxide Brown 9270 (Daichi Seika Kogyo Co., Ltd.) And product name: Daipyroxide Side Brown 9290 (manufactured by Dainichi Seika Kogyo Co., Ltd.).
Specific examples of yellow pigments include monoazo yellow (trade name: Hoster Palm Yellow H3G, manufactured by Hoechst).
Specific examples of the red pigment include iron oxide (trade name: Toda Color 120ED, manufactured by Toda Kogyo Co., Ltd.), quinacridone red (trade name: HostaperRed E2B70, manufactured by Hoechst), and the like.
Specific examples of the blue pigment include phthalocyanine blue (trade name: cyanine blue SPG-8, manufactured by Dainippon Ink & Chemicals, Inc.).
Specific examples of the green pigment include phthalocyanine green (trade name: cyanine green 5310, manufactured by Dainichi Chemical Industries).

  The white pigment is not particularly limited, and specific examples include titanium oxide and zinc white. Titanium oxide can be applied to both rutile type and anatase type, and rutile type titanium oxide is preferably used.

Since hollow particles are excellent in heat insulation, they can be used as light reflecting particles. As the hollow particles, hollow inorganic particles are preferable from the viewpoint of strength and heat insulating properties, and in particular, sunlight or the like can be reflected in the surface layer and shell, and since it has a high long wave emissivity, it is transparent or semi-transparent. Transparent hollow ceramic particles are preferred. Here, the long wave emissivity is the conversion efficiency when the absorbed heat is emitted again as infrared rays. Therefore, when the hollow ceramic particles are contained in the coating film, the temperature increase of the coating film can be effectively suppressed even when the coating film absorbs heat. As described above, the transparent or translucent hollow ceramic particle imparts a high heat shielding effect to the coating film by having reflectivity, heat insulation and radiation. The strength of the hollow ceramic particles in the hollow ceramic particles is preferably 3.9 N / mm ² or more, and the average particle size is preferably about 5 to 150 μm. Examples of the hollow ceramic particles include hollow particles made of a zirconia / titania composite, hollow particles made of a silicon boride ceramic, a shirasu balloon, and a glass balloon.

<Hardened product>
The cured product according to the embodiment of the present invention is obtained by curing the curable resin composition according to the embodiment of the present invention. The curable resin composition according to the present invention or the coating material containing the curable resin composition can be used as a coating material containing the cured product according to the present invention by applying the coating material containing the curable resin composition to a cured material. .

Although it does not specifically limit as a hardening method, The method (method (i)) which adds a component (E) to the resin composition containing the other component except a component (E), the resin liquid (component) which melt | dissolved the component (D) And a method (method (ii)) of mixing a resin liquid (including other components excluding component (D)) in which component (E) is dissolved. When applying by hand, either method (i) or (ii) may be used, and when applying by two-component mixed spray, the blending ratio of the two components is easily stabilized. preferable.

  The hardened | cured material by embodiment of this invention can be hardened and manufactured by leaving still the curable resin composition by embodiment of this invention containing a component (D) and a component (E). Although it does not specifically limit as atmospheric temperature to stand still, 0-50 degreeC is preferable, 5-45 degreeC is more preferable, and 10-40 degreeC is further more preferable. By setting the atmospheric temperature to 0 ° C. or more and 50 ° C. or less, the curability of the curable resin composition is improved. The standing time is not unambiguous because the progress speed of the curing reaction varies greatly depending on the ambient temperature, the amount of component (D), and the amount of component (E), but the standing temperature is 0 to 50 ° C. When the standing time is 0.5 to 30 hours, the curing reaction can be almost completed.

<Other uses>
The curable resin composition according to the embodiment of the present invention can be suitably used for other uses such as a casting material, a binder material, an adhesive, a repair material, and a joint material.

  Specific examples of the casting material include, for example, a light emitting diode module, a mobile phone, a smartphone, a tablet terminal, a personal computer, a camera, an organic electroluminescence (organic EL) device, a flat panel display, a touch panel, electronic paper, a photodiode, and a phototransistor And optical parts such as films, sheets, lenses, optical waveguides, and sealing materials used in solar cells and projectors.

  Specific examples of the binder material include binders such as artificial marble, FRP (Fiber-Reinforced Plastics), and Braille tile.

  Specific examples of adhesives include, for example, glass adhesives, resin adhesives, metal adhesives, etc., and are also used as second generation of acrylic adhesives (SGA). be able to.

  Specific examples of the repair material include concrete repair materials such as crack injection materials and peeling prevention materials, and road repair materials.

  Specific examples of joint materials include tile joint materials, stone joint materials, concrete joint materials, asphalt joint materials, and the like.

  Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited thereto. In this example, “part” means “part by mass”. Measurement and evaluation in this example were performed according to the following methods.

<Mass average molecular weight>
The mass average molecular weight was obtained by dissolving the polymer in tetrahydrofuran as a solvent and converting the molecular weight measured by gel permeation chromatography into polystyrene.

<Viscosity of resin composition>
The viscosity of the resin composition not containing the component (E) as a curing agent was measured. Using a B-type viscometer, it was carried out at 23 ° C. and a rotation speed of 60 rpm.

<Curing time>
In the air at 23 ° C., the resin composition containing components other than the component (E) is blended and mixed with the component (E) to obtain a curable resin composition. A test tube having a thickness of 120 mm was charged up to 70 mm from the bottom. A thermocouple was placed in the curable resin composition in the test tube, and the test tube was left in water at 23 ° C. The temperature change of the curable resin composition after that was measured with the thermocouple. The time until the temperature of the curable resin composition was maximized was defined as the curing time, starting from the time when the component (E) was blended.

<Asphalt adhesion>
On a base material coated with road asphalt (product name “Straight Asphalt 60/80” manufactured by Showa Shell Sekiyu KK) on concrete, a curable resin composition was applied at 23 ° C. to a thickness of 300 μm and cured for 24 hours. did. After curing, the crosscut test described in JISK5600-5-6 was performed, and the adhesion to asphalt was evaluated according to the following criteria.

○: The coating film remained without peeling.
X: The coating film was all peeled off.

<Hardness>
Two sheet-like cured products having a thickness of 3 mm were stacked to a thickness of 6 mm, and the hardness at 23 ° C. was measured using a type D durometer described in JIS K6253.

<Tensile strength>
The dumbbell-shaped No. 1 described in JISK6251 is punched out from a sheet-like cured product with a thickness of 3 mm, a tensile test is performed at a distance between chucks: 50 mm, and a tensile speed: 20 mm / min, and the tensile strength (tensile strength) is measured. did.

[Production Example 1] Production of polymer 1 In a polymerization apparatus equipped with a stirrer, a cooling tube, and a thermometer, 145 parts of deionized water and polyvinyl alcohol (saponification degree: 80%, polymerization degree: 1) as a dispersion stabilizer. 700) 0.5 part was added and stirred.

  After the polyvinyl alcohol is completely dissolved, stirring is stopped, 60 parts of methyl methacrylate, 40 parts of n-butyl methacrylate, 1.3 parts of 2,2′-azobisisobutyronitrile, 1.9 parts of octyl thioglycolate Was added and stirred again. Under stirring, the atmosphere in the polymerization apparatus was replaced with nitrogen, and the temperature was raised to 70 ° C. to carry out polymerization. After detecting the peak of the polymerization exotherm, the temperature was raised to 98 ° C., the reaction was further carried out for 0.5 hours, and the mixture was cooled to 40 ° C.

  The obtained aqueous suspension was filtered through a nylon filter cloth having an opening of 45 μm, and the filtrate was washed with deionized water.

  After dehydration, it was dried at 40 ° C. for 20 hours to obtain a granular (meth) acrylic polymer (hereinafter referred to as “polymer 1”). The weight average molecular weight (Mw) of Polymer 1 was 20,000.

[Production Example 2] Production of polymer 2 In a polymerization apparatus equipped with a stirrer, a cooling pipe and a thermometer, 145 parts of deionized water and polyvinyl alcohol (saponification degree: 80%, polymerization degree: 1) as a dispersion stabilizer. 700) 0.5 part was added and stirred.

  After the polyvinyl alcohol was completely dissolved, stirring was stopped, 100 parts of methyl methacrylate, 0.2 part of 2,2′-azobisisobutyronitrile and 0.9 part of n-dodecyl mercaptan were added and stirred again. Under stirring, the atmosphere in the polymerization apparatus was replaced with nitrogen, and the temperature was raised to 70 ° C. to carry out polymerization. After detecting the peak of the polymerization exotherm, the temperature was raised to 98 ° C., the reaction was further carried out for 0.5 hours, and the mixture was cooled to 40 ° C.

  The obtained aqueous suspension was filtered through a nylon filter cloth having an opening of 45 μm, and the filtrate was washed with deionized water.

  After dehydration, it was dried at 40 ° C. for 20 hours to obtain a granular (meth) acrylic polymer (hereinafter referred to as “polymer 2”). The weight average molecular weight (Mw) of Polymer 2 was 40,000.

[Example 1]
1. Production of curable resin composition In a reaction vessel equipped with a cooler, 70 parts of tetrahydrofurfuryl methacrylate (THFMA) as component (A) and "EXCELATE RUA-049X (trifunctional urethane acrylate) as component (B)" 20 parts, N, N-di (2-hydroxyethyl) -p-toluidine (PTEO) as component (D), 3 parts, paraffin wax, 0.6 parts of “paraffin 130”, “paraffin 150” 0.4 parts, 0.3 part of “HNP-9”, 0.5 part of “Dispalon 230EF” as an antifoaming agent and 0.05 part of “BHT” as an inhibitor were added.

  While stirring these components in the reaction vessel, 10 parts of “Polymer 1” produced in Production Example 1 was added as component (C).

  Next, the solution in the reaction vessel was heated to 75 ° C. and stirred for 2 hours while maintaining the temperature. After confirming that the polymer 1 and the paraffin wax were completely dissolved, the mixture was cooled to 40 ° C., and “BYK-S780” which is a paraffin wax dispersion was added and stirred for 30 minutes.

  Thereafter, the solution in the reaction vessel was brought to 23 ° C., and 1 part of “Nikka Octix Cobalt (8%)” (product name) was added as the component (D). The mixture was further stirred for 30 minutes to obtain a resin composition.

  A curable resin composition was obtained by adding 3 parts of “Nyper NS” (product name) as a component (E) to the obtained resin composition, followed by stirring.

2. Manufacture of sheet-like cured product for evaluation A curable resin composition obtained by vacuum defoaming in a glass cell made of two sheet glass coated with a release PET film on the surface in contact with the curable resin composition and a vinyl chloride gasket. The product was poured and cured at 23 ° C. for 12 hours. After curing, the plate glass and the PET film were removed to obtain a sheet-like cured product for evaluation having a length of 250 mm, a width of 250 mm, and a thickness of 3 mm.

  The viscosity of the resin composition, the curing time of the curable resin composition, and the asphalt adhesion, hardness, and tensile strength of the cured product were evaluated. The results are shown in Table 1.

[Examples 2 to 47]
A resin composition, a curable resin composition, and a sheet-like cured product for evaluation having a thickness of 3 mm were prepared in the same manner as in Example 1 except that the compositions were changed as shown in Table 1, Table 2, and Table 3. Went. The results are shown in Table 1, Table 2 and Table 3.

[Comparative Examples 1 and 2]
In Comparative Examples 1 and 2, as shown in Table 1, a resin composition, a curable resin composition, and a curable resin composition were used in the same manner as in Example 1 except that a bifunctional urethane acrylate was used instead of the component (B). A sheet-like cured product for evaluation having a thickness of 3 mm was prepared and evaluated. The results are shown in Table 1, Table 2 and Table 3.

  As shown in Table 1, Table 2, and Table 3, Examples 1 to 47 all had good curing time of the curable resin composition, asphalt adhesion of the cured product, hardness, and tensile strength. On the other hand, since the comparative examples 1 and 2 had a long curing time, the asphalt adhesion of the cured product was poor. Moreover, the hardness and tensile strength of the cured product were also low.

Abbreviations in the table are as follows.
THFMA: Tetrahydrofurfuryl methacrylate, manufactured by Mitsubishi Chemical Corporation, acrylate ester THF (trade name).
FA-512M: 2-dicyclopentenoxyethyl methacrylate, manufactured by Hitachi Chemical Co., Ltd., funkrill FA-512M (trade name).
Light ester PO (trade name): Phenoxyethyl methacrylate, manufactured by Kyoeisha Chemical Co., Ltd.
BZMA: benzyl methacrylate, manufactured by Mitsubishi Chemical Corporation, Acryester BZ (trade name).
ETMA: 2-ethoxyethyl methacrylate, manufactured by Mitsubishi Chemical Corporation, Acryester ET (trade name).
2-HPMA: 2-hydroxypropyl methacrylate, manufactured by Mitsubishi Chemical Corporation, Acryester HP (trade name).
EXCERATE RUA-049X (product name): Trifunctional urethane acrylate, manufactured by Asia Industrial Co., Ltd.
EXCERATE RUA-048 (product name): Trifunctional urethane acrylate, manufactured by Asia Industrial Co., Ltd.
EXCERATE RX12-89 (product name): pentafunctional urethane acrylate, manufactured by Asia Industrial Co., Ltd.
EXCERATE RUA-075 (product name): pentafunctional urethane acrylate, manufactured by Asia Industrial Co., Ltd.
EXCERATE RUA-071 (product name): 6-functional urethane acrylate, manufactured by Asia Industrial Co., Ltd.
EXCERATE RUA-076MG (product name): 6-functional urethane acrylate, manufactured by Asia Industrial Co., Ltd.
EXCERATE RUA-077 (product name): 10 functional urethane acrylate, manufactured by Asia Industrial Co., Ltd.
Polymer 1: Polymer produced in Production Example 1, copolymer of methyl methacrylate / n-butyl methacrylate = 60/40 (monomer mass ratio), Mw = 20,000.
Polymer 2: Polymer produced in Production Example 2, polymethyl methacrylate, Mw = 40,000.
PTEO: N, N-di (2-hydroxyethyl) -p-toluidine, manufactured by Nippon Emulsifier Co., Ltd.
Nikka Octix Cobalt (product name) (8%): 8% solution of cobalt 2-ethylhexanoate, manufactured by Nippon Chemical Industry Co., Ltd.
Nyper NS (product name): Suspension of dibenzoyl peroxide (purity 40%), manufactured by NOF Corporation.
NK Oligo UA-4200 (product name): bifunctional urethane acrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.
NK Oligo U-200PA (product name): bifunctional urethane acrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.
New Frontier BPE-4 (product name): EO-modified bisphenol A diacrylate (total number of repetitions of EO (ethylene oxide) part in the molecule n≈4), manufactured by Daiichi Kogyo Seiyaku.
NK ester APG-700 (product name): polypropylene glycol diacrylate (repetition number of propylene glycol part n≈12), manufactured by Shin-Nakamura Chemical Co., Ltd.
NK ester NPG (product name): Neopentyl glycol dimethacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.
NK ester DCP (product name): tricyclodecane dimethanol di (meth) acrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.
Light ester 1,9ND (product name): 1,9-nonanediol dimethacrylate, manufactured by Kyoeisha Chemical Co., Ltd.
Acryester TMP (product name): trimethylolpropane tri (meth) acrylate, manufactured by Mitsubishi Chemical Corporation.
Paraffin wax 130 (product name): Paraffin wax (melting point in the catalog: 55 ° C.), manufactured by Nippon Seiwa Co., Ltd.
Paraffin wax 150 (product name): Paraffin wax (melting point in the catalog: 66 ° C.), manufactured by Nippon Seiwa Co., Ltd.
HNP-9 (product name): paraffin wax (melting point described in the catalog: 75 ° C.), manufactured by Nippon Seiwa Co., Ltd.
BYK-S780 (product name): Petroleum naphtha dispersion with 10% paraffin wax, manufactured by Big Chemie Japan.
Disparon 230EF (product name): Defoamer, manufactured by Enomoto Kasei Co., Ltd.
BHT: 2-6-di-t-butyl-4-methylphenol, polymerization inhibitor, manufactured by Honshu Chemical Co., Ltd., H-BHT (trade name).

  According to an embodiment of the present invention, a curable resin composition, a cured product thereof, and a curable resin composition capable of obtaining a cured product having a short curing time, excellent adhesion to asphalt, hardness, and tensile strength. Since it can provide the coating material containing, it is very useful industrially.

Claims (8)

  Curing containing monofunctional (meth) acrylate (A), trifunctional or higher urethane (meth) acrylate (B), (meth) acrylic polymer (C), reducing agent (D), curing agent (E) Resin composition. 30 to 90% by mass of component (A), 1 to 40% by mass of component (B), and 0.1 to 0.4% of component (C) with respect to 100% by mass in total of components (A), (B) and (C). 1-30% by mass,
The component (A), (B), and 0.1 to 10 parts by mass of the component (E) and 0.1 to 10 parts by mass of the component (E) with respect to 100 parts by mass in total. The curable resin composition according to 1. Component (A) includes (meth) acrylate having a cyclic structure,
Component (B) is a urethane (meth) acrylate having 3 to 10 (meth) acryloyl groups in the molecular structure,
The curable resin composition of Claim 1 or 2 whose component (C) is a polymer containing the unit of a monofunctional (meth) acrylic-type monomer. Component (D) includes aromatic tertiary amines and metal soaps,
Examples of the aromatic tertiary amines include N, N-dimethyl-p-toluidine, N, N-diethyl-p-toluidine, N, N-di (2-hydroxyethyl) -p-toluidine, N, N-di. Including at least one selected from (2-hydroxypropyl) -p-toluidine,
As the metal soaps, including at least one selected from cobalt naphthenate, copper naphthenate, manganese naphthenate, cobalt octylate, vanadyl acetylacetonate,
The curable resin composition according to any one of claims 1 to 3, wherein the component (E) contains dibenzoyl peroxide.   The coating material containing the curable resin composition in any one of Claim 1 to 4.   A road paint containing the curable resin composition according to claim 1.   The thermal barrier coating material for roads containing the curable resin composition in any one of Claim 1 to 4.   Hardened | cured material of the curable resin composition in any one of Claim 1 to 4.