JP6764249B2 - Curable resin composition, cured product thereof, and coating material - Google Patents

Description

The present invention relates to a curable resin composition, a cured product thereof, and a coating material comprising the composition.

A room temperature curable (meth) acrylic resin composition using benzoyl peroxide as a curing agent and tertiary amine as a curing accelerator can be used as a binder material for molded products such as coating materials, adhesives, and artificial marble. Widely used. However, such a room temperature curable (meth) acrylic resin composition is difficult to adapt to a colorless transparent material because the cured product is colored due to the influence of products derived from the curing agent and the curing accelerator. there were.

As a method for solving this problem, for example, Patent Document 1 discloses a (meth) acrylic resin composition containing a hydroperoxide as a curing agent and a thiourea compound as a curing accelerator, which can be cured at room temperature. , It is said that a colorless and transparent cured product can be provided.

Further, Patent Document 2 discloses a (meth) acrylic resin composition containing peroxymonocarbonates such as t-hexyl peroxyisopropyl monocarbonate as a curing agent and a thiourea compound as a curing accelerator. It is said that a cured product having excellent strength and transparency can be obtained by curing at room temperature.

JP-A-2011-32315 International Publication No. 2012/137869

However, in the combination of the curing agent and the curing accelerator as disclosed in Patent Documents 1 and 2, the polymerization reaction does not proceed sufficiently at room temperature in the presence of oxygen, and therefore, when used as a coating material, curing is poor. It happened to be.

The present invention provides a curable resin composition having good curability at room temperature even in the presence of oxygen, and a cured product having excellent hardness, a cured product thereof, and a coating material composed of the composition. The purpose.

According to one aspect of the invention
(A) Radical-polymerizable vinyl-based monomer component,
(B) Thiourea compound component,
(C) A curable resin composition containing a peroxide component having the structure of the following formula (1) and an organic phosphorus compound component other than the components (D) and (A) is provided.

(In formula (1), R is a hydrocarbon group having 1 to 15 carbon atoms.)

According to another aspect of the present invention, a cured product of the above curable resin composition is provided.

According to another aspect of the present invention, a coating material composed of the above-mentioned curable resin composition is provided.

According to the present invention, there is provided a curable resin composition which has good curability at room temperature even in the presence of oxygen and can obtain a cured product having excellent hardness, a cured product thereof, and a coating material composed of the composition. be able to.

In the present specification, "(meth) acrylic" is a general term for acrylic and methacrylic, "(meth) acrylate" is a general term for acrylate and methacrylate, and "(meth) acryloyl group" is a general term for acryloyl group and methacrylic. It is a general term for groups, and CH ₂ = C (R) -C (= O)-[R is a hydrogen atom or a methyl group. ] Is represented.

<Curable resin composition>
The curable resin composition according to the embodiment of the present invention comprises (A) a radically polymerizable vinyl-based monomer component, (B) a thiourea compound component, and (C) a peroxide component having a structure of the formula (1). And contains organic phosphorus compound components other than the components (D) and (A). The curable resin composition according to the embodiment of the present invention may further contain the (E) (meth) acrylic polymer component as an optional component.

In this specification, the structure of (A) radically polymerizable vinyl-based monomer component is “(A) component”, (B) thiourea compound component is “(B) component”, and (C) formula (1). The peroxide component having is "(C) component", the organic phosphorus compound component other than the (D) and (A) components is "(D) component", and the (E) (meth) acrylic polymer component is "(( E) Ingredients.

In the curable resin composition according to the embodiment of the present invention, the contents of the component (A) and the component (E) do not include the total mass (the component (E)) of the component (A) and the component (E), respectively. In this case, the mass of the component (E) is zero. The same applies hereinafter.) It is preferable that the component (A) is 5 to 100% by mass and the component (E) is 0 to 95% by mass. From the viewpoint of obtaining the characteristics of the desired cured product derived from the component (A) and the viscosity of the composition, the content of the component (A) is 50% by mass or more (that is, the component (E) is 0 to 50% by mass). Preferably, the component (A) is 60% by mass or more (that is, the component (E) is 0 to 40% by mass), and the component (A) is 65% by mass or more (that is, the component (E) is 0 to 35% by mass). Is particularly preferable.

[(A) component]
The radically polymerizable vinyl-based monomer as the component (A) is a compound having a radically polymerizable vinyl group. It may be a monofunctional compound having one radically polymerizable vinyl group in the molecular structure, or it may be a polyfunctional compound having two or more radically polymerizable vinyl groups in the molecular structure. Examples of the component (A) include a monofunctional (meth) acrylic monomer, a polyfunctional (meth) acrylic monomer, and other vinyl group-containing monomers.

Specific examples of the monofunctional (meth) acrylic monomer include (meth) acrylic acid, 2- (meth) acryloyloxyethyl succinate, 2- (meth) acryloyloxyethyl maleate, and 2- (meth) acryloyl phthalate. (Meta) acrylate containing a carboxyl group such as oxyethyl, 2- (meth) acryloyloxyethyl hexahydrophthalate; 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) ) Alkyl (meth) acrylates such as acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate; cyclohexyl (meth) Meta) 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, nonylphenoxypolyethylene glycol (meth) acrylate, phenoxypolypropylene glycol (meth) acrylate, phenylphenyl ( Meta) acrylate, phenylphenoxyethyl (meth) acrylate, phenoxybenzyl (meth) acrylate, phenylbenzyl (meth) acrylate, naphthyl (meth) acrylate, (1-naphthyl) methyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate , (Meta) acrylate containing a cyclic structure such as glycidyl (meth) acrylate and (meth) acryloylmorpholine; alkoxy (meth) such as methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate and butoxyethyl (meth) acrylate. ) Acrylate; 3- (meth) acryloxipropi Examples thereof include rutrimethoxysilane, 3- (meth) acryloxipropyltriethoxysilane, 2- (meth) acryloyloxyethyl acid phosphate, trifluoroethyl (meth) acrylate and heptadecafluorodecyl (meth) acrylate.

Specific examples of the polyfunctional (meth) acrylic monomer include ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, and butylene glycol di ( Meta) acrylate, polybutylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, tricyclodecandy Methanoldi (meth) acrylate, polycarbonate diol di (meth) acrylate, polyester diol di (meth) acrylate, bisphenol A ethylene oxide adduct di (meth) acrylate, bisphenol A propylene oxide adduct di (meth) acrylate, polyurethane di (meth) Bifunctional (meth) acrylates such as meta) acrylates; trimethylolpropantri (meth) acrylates, tri (meth) ethoxylated isocyanurates, ε-caprolactone-modified tris ((meth) acloxyethyl) isocyanurate, etc. Functional (meth) acrylate; tetrafunctional (meth) acrylate such as ditrimethylolpropantetra (meth) acrylate; pentafunctional (meth) acrylate such as dipentaerythritol penta (meth) acrylate; dipentaerythritol hexa (meth) Examples thereof include hexafunctional (meth) acrylates such as acrylates.

Examples of other vinyl group-containing monomers include styrene, α-methylstyrene, acrylonitrile, vinyl acetate and the like.

These radically polymerizable vinyl-based monomers may be used alone or in combination of two or more.

It is not particularly limited because it depends on the required properties of the coating material according to the embodiment of the present invention, but since the curable resin composition has good curability, it is an alkyl (meth) acrylate or a (meth) acrylate containing a cyclic structure. Is preferably used as the component (A). Among them, in terms of the hardness of the cured product, methyl (meth) acrylate, dicyclopentenyl (meth) acrylate, 2-dicyclopentenoxyethyl (meth) acrylate, benzyl (meth) acrylate, and phenoxyethyl (meth) It is preferable to use acrylate or tetrahydrofurfuryl (meth) acrylate. Further, it is preferable to use a monofunctional (meth) acrylate and a polyfunctional (meth) acrylate in combination.

[Component (B)]
The thiourea compound as the component (B) is a curing accelerator and reacts with the component (C) to generate radicals.

Specific examples of the component (B) include thiourea, ethylenethiourea, N, N'-dimethylthiourea, N, N'-diethylthiourea, N, N'-dipropylthiourea, N, N'-dibutylthiourea, N, Examples thereof include N'-dilaurylthiourea, N, N'-diphenylthiourea, trimethylthiourea, 1-acetyl-2-thiourea, 1-benzoyl-2-thiourea and the like.

As the component (B), one type may be used alone, or two or more types may be used in combination.

As the component (B), N, N'-diethylthiourea and N, N'-di-butylthiourea are particularly preferable from the viewpoint of the hardness of the cured product.

The blending amount of the component (B) is preferably 0.05 to 5 parts by mass, more preferably 0.1 to 4 parts by mass, when the total amount of the component (A) and the component (E) is 100 parts by mass. , More preferably 0.2 to 3 parts by mass. When the amount is 0.05 parts by mass or more, the curability of the curable resin composition according to the embodiment of the present invention becomes good. By setting the content to 5 parts by mass or less, the hardness of the cured product according to the embodiment of the present invention becomes good.

[Component (C)]
The peroxide containing the structure of the following formula (1), which is the component (C), is a curing agent and reacts with the component (B) to generate radicals.

In formula (1), R is a hydrocarbon group having 1 to 15 carbon atoms. R may be saturated or unsaturated, linear or branched or cyclic. From the viewpoint of solubility in the component (A), R is preferably a hydrocarbon group having 4 to 8 carbon atoms, more preferably a saturated hydrocarbon group having 4 to 8 carbon atoms, and saturated with 4 to 8 carbon atoms. It is preferably a branched hydrocarbon group.

Specific examples of the component (C) include t-hexyl peroxyisopropyl carbonate, t-butylperoxyisopropyl carbonate, t-butylperoxy2-ethylhexyl carbonate, t-butylperoxyallyl monocarbonate, and 1,6-bis. Examples thereof include (t-butylperoxycarbonyloxy) hexane, t-amylperoxyisopropyl carbonate, and t-amylperoxy2-ethylhexyl carbonate.

As the component (C), one type may be used alone, or two or more types may be used in combination.

The components (C) include t-hexyl peroxyisopropyl carbonate, t-butylperoxyisopropyl carbonate, 1,6-bis (t-butylperoxycarbonyloxy) hexane, and t- from the viewpoint of hardness of the cured product. Amylperoxyisopropyl carbonate and t-amylperoxy2-ethylhexyl carbonate are particularly preferable.

When the total amount of the component (A) and the component (E) is 100 parts by mass, the blending amount of the component (C) is preferably 0.1 to 10 parts by mass, more preferably 0.3 to 7 parts by mass. 0.5 to 5 parts by mass is more preferable. By setting the blending amount of the component (C) to 0.1 parts by mass or more, the curability of the curable resin composition according to the embodiment of the present invention becomes good. By setting the blending amount of the component (C) to 10 parts by mass or less, the hardness of the cured product according to the embodiment of the present invention becomes good.

[Component (D)]
(D) a component (A) organophosphorus compound other than the component is to improve the curability of the curable resin composition in the presence of oxygen, it is a component to improve the hardness of the cured product.

Specific examples of the component (D) include triphenylphosphine, trisnonylphenylphosphine, tricresylphosphine, diphenylmono (2-ethylhexyl) phosphine, diphenylmonodecylphosphine, diphenylhydrogenphosphine, and tetraphenyl. Dipropylene glycol diphosphine, tetra (C12-15 alkyl) -4,4'-isopropyridendiphenyldiphosphine, triethylphosphine, tris (2-ethylhexyl) phosphine, tridecylphosphine, trilaurylphosphine, Trilaurylthiophosphine, tris (tridecyl) phosphine, trioleylphosphine, diethylhydrogenphosphine, bis (2-ethylhexyl) hydrogenphosphine, dilaurylhydrogenphosphine, dioleylhydrogenphosphine, bis (decyl) penta Phosphite compounds such as erythritol diphosphine; triphenylphosphine, trioltotrilphosphine, trimetatrilphosphine, tripalatrilphosphine, trisorthomethoxyphenylphosphine, trismethmethoxyphenylphosphine, trisparamethoxyphenylphosphine, diphenylcyclohexylphosphine, Tricyclohexylphosphine, tri-n-butylphosphine, tri-i-butylphosphine, tri-t-butylphosphine, tri-n-octylphosphine, parastyryldiphenylphosphine, di-t-butyl (2-butenyl) phosphine, di Phosphine compounds such as -t-butyl (3-methyl-2-butenyl) phosphine, [4- (N, N-dimethylamino) phenyl] di-t-butylphosphine; trimethylphosphate, triethylphosphate, triphenylphosphine, tri Cresyl phosphate, trixylenyl phosphate, cresil diphenyl phosphate, tris (chloropropyl) phosphate, tris (tribromoneopentyl) phosphate, ethyl acid phosphate, butyl acid phosphate, dibutylpyroacid phosphate, toxiethyl acid phosphate, 2- Ethylhexyl acid phosphate, alkyl (C12, C14, C16, C18) acid phosphate, isodecyl acid phosphate, oleyl acid phosphate, tetracosyl acid phosphate, ethylene Phosphate compounds such as glycol acid phosphate; phosphonate compounds such as ethyl diethylphosphonoacetate, diethylbenzylphosphonate, diethyl (p-chlorobenzyl) phosphonate can be mentioned.

As the component (D), one type may be used alone, or two or more types may be used in combination.

As the component (D), a phosphine compound and a phosphine compound are preferable from the viewpoint of curability of the curable resin composition, and particularly triethylphosphite and tris (2-ethylhexyl) phosphite from the viewpoint of hardness of the cured product. Tridecylphosphite, trilaurylphosphite, trilaurylthiophosphite, tris (tridecyl) phosphite, trioleylphosphine, and triphenylphosphine are preferred.

When the total amount of the component (A) and the component (E) is 100 parts by mass, the blending amount of the component (D) is preferably 0.1 to 10 parts by mass, more preferably 0.3 to 7 parts by mass. 0.5 to 4 parts by mass is more preferable. By setting the blending amount of the component (D) to 0.1 parts by mass or more, the curability of the curable resin composition becomes good. By setting the blending amount of the component (D) to 10 parts by mass or less, the hardness of the cured product becomes good.

[(E) component]
The (meth) acrylic polymer as the component (E) is an optional component, but the curability of the curable resin composition can be improved by further adding the component (E).

This (meth) acrylic polymer is a polymer containing 50% by mass or more of (meth) acrylic monomer units in its composition. The unit is a repeating unit constituting the polymer.

Specific examples of the (meth) acrylic monomer used for the component (E) include monofunctional (meth) acrylic monomers and polyfunctional (meth) acrylic monomers cited as specific examples of the component (A). Can be mentioned. A monofunctional (meth) acrylic monomer is preferable from the viewpoint of solubility in the component (A).

The (meth) acrylic monomer unit contained in the component (E) may be one kind or two or more kinds.

Further, the component (E) may contain a monomer unit other than the (meth) acrylic monomer unit. The other monomer may be a monomer copolymerizable with a (meth) acrylic monomer, and examples thereof include vinyl monomers such as styrene, α-methylstyrene, acrylonitrile, and vinyl acetate.

The ratio of the (meth) acrylic monomer unit in the component (E) is preferably 70% by mass or more, more preferably 80% by mass or more. The upper limit of this ratio is not particularly limited and may be 100% by mass.

The component (E) is used in a state of being dissolved in the component (A) in the curable resin composition according to the embodiment of the present invention. Examples of the method for dissolving the component (A) include stirring at room temperature and stirring under heating. Since it can be dissolved in a short time, stirring under heating is particularly preferable, and in that case, it is preferably carried out at 40 to 100 ° C. for 0.5 to 5 hours.

In the curable resin composition according to the embodiment of the present invention, the content of the component (E) is 1 when the total amount of the component (A) and the component (E) is 100% by mass. The content of the component (A) is preferably 50 to 99% by mass, and the content of the component (E) is more preferably 2% to 40% by mass (therefore, the content of the component (A) is preferably 50 to 99% by mass). The content of the component is more preferably 60 to 98% by mass), the content of the component (E) is more preferably 3% by mass to 35% by mass (therefore, the content of the component (A) is further preferably 65 to 97% by mass). preferable). By setting the content of the component (E) to 1% by mass or more, the curability of the curable resin composition can be improved. Moreover, the strength of the cured product can be improved. By setting the content of the component (E) to 50% by mass or less, the viscosity becomes appropriate and the workability of the coating material becomes good.

Preferred specific examples of the component (E) include polymethylmethacrylate, polyethylmethacrylate, polybutylmethacrylate, a copolymer composed of a methylmethacrylate unit and an n-butylmethacrylate unit, and a methylmethacrylate unit and an n-butylacrylate unit. And the like. Among these, a copolymer composed of a methyl methacrylate unit and an n-butyl methacrylate unit is preferable from the viewpoint of solubility in the component (A) and transparency of the cured product.

The mass average molecular weight of the component (E) is preferably 10,000 to 500,000, more preferably 30,000 to 200,000. When the mass average molecular weight is 10,000 or more, the hardness of the cured product is good. When it is 500,000 or less, the solubility in the component (A) becomes good.

[Other ingredients]
The curable resin composition according to the embodiment of the present invention may contain other components as long as the effects of the present invention are not impaired. The content of the other components is not particularly limited, but is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, based on 100 parts by mass of the total of the components (A) to (E).

Specific examples of other components include addition of paraffin wax, rubber, plasticizer, antioxidant, UV absorber, aggregate, pigment, rocking agent, defoaming agent, polymerization inhibitor, silane coupling agent, etc. Agents and the like can be mentioned. In order to further improve the curability of the curable resin composition, a thermal polymerization initiator such as a peroxide or an azo compound other than the component (C) or a radical polymerization initiator such as a photopolymerization initiator may be added.

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 by oxygen. It is preferable to use two or more kinds of paraffin wax having different melting points in combination. The melting point of the paraffin wax is preferably 40 to 80 ° C. Specific examples of paraffin wax include paraffin 115 (melting point described in the catalog: 47 ° C., manufactured by Nippon Seiwa Co., Ltd.), paraffin 130 (melting point described in the catalog: 55 ° C., manufactured by Nippon Seiwa Co., Ltd.), paraffin 150 (described in the catalog). Melting point: 66 ° C., manufactured by Nippon Seiwa Co., Ltd.) and the like. When the melting point of the paraffin wax is 40 ° C. or higher, a sufficient air blocking action is obtained when the curable resin composition is cured, and the surface curability is good. On the other hand, when the melting point of the paraffin wax is 80 ° C. or lower, the solubility of the paraffin wax in the curable resin composition becomes good when the resin composition is prepared. Further, by using paraffin waxes having different melting points in combination, a sufficient air blocking action can be obtained even when the temperature changes, and the surface curability becomes good. When used in combination, it is preferable to use those 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 terms of improving the surface curability. It is preferable that the wax is dispersed in an organic solvent and the particle size of the dispersed wax is finely divided into 0.1 μm to 50 μm. Thereby, the air blocking action can be effectively exhibited. The dispersed paraffin wax is commercially available, and the wax can be added as it is.

Rubber may be added to the curable resin composition according to the embodiment of the present invention in order to improve the strength and elongation of the cured product. Specific examples of the rubber include (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 deterioration of the cured product. Specific examples of antioxidants include n-octadecyl-3- (3', 5'-di-t-butyl-4'-hydroxyphenyl) propionate and 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 [ Phenolic antioxidants such as 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate]; dihexyl sulfide, dilaurilu 3,3'-thiodipropionate, ditridecyl-3,3'-thio Examples thereof include sulfur-based antioxidants such as dipropionate, dimyristyl-3,3'-thiodipropionate, disterialu 3,3'-thiodipropionate, and pentaerythritol tetrakis (β-laurylthiopropionate).

A plasticizer may be added to the curable resin composition according to the embodiment of the present invention in order to improve the elongation of the cured product. Specific examples of the plasticizer include phthalates such as dibutyl phthalate, di2-ethylhexyl phthalate and diisodecyl phthalate, adipic acid esters such as di-2-ethylhexyl adipate and octyl adipate, dibutyl sebacate and di Examples thereof include sebacic acid esters such as -2-ethylhexyl sebacate, dibasic fatty acid esters such as azeline esters such as di-2-ethylhexyl azelate and octyl azelate; and paraffins such as chlorinated paraffin.

An ultraviolet absorber may be added to the curable resin composition according to the embodiment of the present invention in order to suppress photodegradation of the cured product. Specific examples of the ultraviolet absorber include 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-octyloxybenzophenone, 2-hydroxy-4-decyloxybenzophenone, 2-hydroxy-4,4'-dimethoxybenzophenone, 2-. Derivatives of 2-hydroxybenzophenone such as hydroxy-4,4'-dibutoxybenzophenone or 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3', 5'- Ditashaly butylphenyl) benzotriazole or halides thereof or phenylsalicylate, p-tersary butylphenylsalicylate and the like can be mentioned.

The curable resin composition according to the embodiment of the present invention may be used as a mortar composition by blending an aggregate. Specific examples of aggregates include sand, silica 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, and glass. Examples include powder, ceramic aggregate, pottery scraps, colored aggregate and the like.

The curable resin composition according to the embodiment of the present invention may contain a pigment for coloring. Specific examples of the pigment include organic pigments such as azo pigments and phthalocyanine pigments; inorganic pigments such as ceramic pigments, iron oxide and titanium oxide.

A rocking agent may be added to the curable resin composition according to the embodiment of the present invention in order to suppress sedimentation when an aggregate or pigment is blended. Specific examples of the shaking agent include an organic shaking agent such as urethane urea, fatty acid amide, organic bentonite, polyethylene oxide wax, and organically modified sepiolite, and an inorganic shaking agent such as fine particle silica.

A defoaming agent may be added to the curable resin composition according to the embodiment of the present invention in order to remove air bubbles in the curable resin composition. Specific examples of the defoaming agent include an acrylic defoaming agent in which a special acrylic polymer is dissolved in a solvent, a vinyl defoaming agent in which a special vinyl polymer is dissolved in a solvent, and the like. Specific product names of defoamers include the Disuparon series manufactured by Kusumoto Kasei Co., 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, LF-1980, LF-1982, LF-1983, LF-1984, LF-1985, etc.) and Big Chemie. -Examples include BYK-052 and BYK-1752 manufactured by Japan.

A polymerization inhibitor may be added to the curable resin composition according to the embodiment of the present invention in order to improve storage stability. 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 the aggregate and the filler. Specific examples of the silane coupling agent include 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 3- (glycidoxypropyl) trimethoxysilane, and 3-mercaptopropyl. Examples thereof include trimethoxysilane and 3-aminopropyltriethoxysilane.

A thermosetting initiator other than the component (C) may be added to the curable resin composition according to the embodiment of the present invention in order to improve the curability. Specific examples of the thermal polymerization initiator include ketone peroxides such as methyl ethyl ketone peroxide; 1,1-di (t-hexylperoxy) -3,3,5-trimethylcyclohexane, and 1,1-di (t-hexyl). Peroxyketals such as peroxy) cyclohexane and 1,1-di (t-butylperoxy) cyclohexane; dialkyl peroxides such as dicumyl peroxide and di-t-butyl peroxide; diacylpers such as dilauroyl peroxide. Oxide; peroxydicarbonate such as di (4-t-butylcyclohexyl) peroxydicarbonate, di (2-ethylhexyl) peroxydicarbonate; t-butylperoxy-2-ethylhexanoate, t-butylper Peroxides such as oxybenzoate, peroxyesters such as 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate and 2,2'-azobisisobutyronitrile, 2,2' -Azobis (2-methylbutyronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 1,1'-azobis-1-cyclohexanecarbonitrile, dimethyl-2,2'-azobisiso Examples thereof include azo compounds such as butylate, 4,4'-azobis-4-cyanovaleric acid, and 2,2'-azobis- (2-amidinopropane) dihydrochloride.

A photopolymerization initiator may be added to the curable resin composition according to the embodiment of the present invention in order to improve the curability. Specific examples of the photopolymerization initiator include benzophenone-type compounds such as benzophenone, 4-methylbenzophenone, 2,4,6-trimethylbenzophenone, methyl orthobenzoylbenzoate, and 4-phenylbenzophenone; t-butylanthraquinone, 2-ethyl. Anthraquinone-type compounds such as anthraquinone; 2-hydroxy-2-methyl-1-phenylpropan-1-one, oligo {2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone}, Benzyl dimethyl ketal, 1-hydroxycyclohexylphenyl ketone, benzoyl 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 other alkylphenone-type compounds; 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, Thioxanthone-type compounds such as diethylthioxanthone and isopropylthioxanthone; 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, bis (2,4) Examples thereof include acylphosphine oxide-type compounds such as 6-trimethylbenzoyl) -phenylphosphine oxide; and phenylglycolate-type compounds such as phenylglycoxylic acid methyl ester.

As for other components, one type may be used alone, or two or more types may be used in combination.

〔Production method〕
The method for producing the curable resin composition according to the embodiment of the present invention is not particularly limited, but from the viewpoint of workability, the components (A) and (D) may be mixed or mixed in advance, or the components (A) and (D) may be produced. It is preferable to stir and mix the components and the component (E) to prepare a resin solution. When the component (E) is not used, it is preferable to stir and mix the components (A) and (D) at room temperature or at about 40 to 80 ° C. for 1 to 30 minutes. When the component (E) is used, it is preferable to stir and mix the component (A), the component (D) and the component (E) under heating at about 40 to 100 ° C. for 0.5 to 5 hours.

The component (B) may be mixed at the same time when the components (A) and (D) are mixed and stirred, or when the components (A), (D) and (E) are stirred and mixed, or a curable resin. Immediately before the composition is cured, it may be stirred and mixed with the resin solution at room temperature. From the viewpoint of storage stability of the curable resin composition, the component (C) is preferably stirred and mixed at room temperature immediately before the curable resin composition is cured.

[Action effect]
The curable resin composition according to the embodiment of the present invention is a peroxide containing the component (B) which is an accelerator, that is, the thiourea compound and the component (C) which is a curing agent, that is, the structure of the formula (1). Is combined. By further adding the organic phosphorus compound as the component (D) to such a specific combination of polymerization initiation systems, a cured product having good curability that becomes tack-free at room temperature and having excellent hardness can be obtained. A curable resin composition can be obtained.

<Cured 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 curing method is not particularly limited, but is a method of adding the component (C) to a resin solution in which the component (B) is dissolved (including other components other than the component (C)), and a resin solution in which the component (C) is dissolved. A method of adding the component (B) to (including other components excluding the component (B)), a resin solution in which the component (B) is dissolved (including other components excluding the component (C)) and the component (C). Examples thereof include a method of mixing with a dissolved resin solution (including other components other than the component (B)). From the viewpoint of workability and storage stability, the method of adding the component (C) to the resin solution in which the component (B) is dissolved is preferable.

The cured product according to the embodiment of the present invention is produced by curing the curable resin composition according to the embodiment of the present invention containing all the components including the component (B) and the component (C) by allowing it to stand. Can be done. The ambient temperature to be allowed to stand is not particularly limited, but is preferably 5 to 45 ° C, more preferably 10 to 40 ° C, still more preferably 25 to 35 ° C. By setting the ambient temperature to 5 ° C. or higher, the curability of the curable resin composition becomes good. In addition, the hardness of the cured product becomes good. By setting the ambient temperature to 45 ° C. or lower, the time until curing becomes long, and coating work and the like can be easily performed. The standing time cannot be unequivocally determined because the progress rate of the curing reaction varies greatly depending on the ambient temperature, the amount of the component (B), and the amount of the component (C), but the standing temperature is 5 to 45 ° C. When the standing time is 0.5 to 30 hours, the curing reaction is almost completed.

<Coating material>
The curable resin composition according to the embodiment of the present invention has good curability at room temperature even in the presence of oxygen, and a cured product having excellent hardness can be obtained, so that it can be suitably used as a coating material.

Specific examples of coating materials include coating materials for civil engineering and construction such as wall paints, floor paints, roof paints, bridge paints, plant paints, iron structure paints, and concrete paints, and non-slip paints. And drainage paints, heat shield paints, road marking paints, road coating materials such as floor slab waterproofing paints, furniture coating materials, decorative coating materials, electronic equipment / mobile coating materials, home appliance coating materials, etc. Examples thereof include waterproof coating materials, automobile coating materials, motorcycle coating materials, heavy machinery coating materials, railroad vehicle coating materials, and marine coating materials.

Further, the curable resin composition according to the embodiment of the present invention can be suitably used as a casting material, a binder material, an adhesive, a repair material, and a joint material.

Specific examples of casting materials include 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, and phototransistors. , Films, sheets, lenses, optical waveguides, optical components such as encapsulants used in solar cells, projectors and the like.

Specific examples of the binder material include binders such as artificial marble, FRP, and Braille tile.

Specific examples of the adhesive include, for example, an adhesive for glass, an adhesive for resin, and an adhesive for metal. In particular, since the (meth) acrylic resin has excellent adhesiveness, it can be suitably used as an adhesive for (meth) acrylic resin such as for a (meth) acrylic water tank. It can also be used as a second generation acrylic adhesive (SGA).

Specific examples of the repair material include a repair material for concrete and a repair material for roads.

Specific examples of the joint material include a joint material for tiles, a joint material for stone materials, a joint material for concrete, and a joint material for asphalt.

Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited thereto. In this embodiment, "part" means "part by mass". The measurement and evaluation in this example were carried out according to the following method.

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

(Evaluation of curability)
A 10 cm × 15 cm frame was provided on the PET film with a urethane sponge having a thickness of 2 mm and a pressure-sensitive adhesive, and the curable resin composition was poured into the frame so as to have a thickness of about 2 mm. Starting from the time when the component (C) was blended, the tack on the surface of the curable resin composition poured into the frame was confirmed at each time. Curability was evaluated according to the following criteria.

◯: It became tack-free in less than 2 hours.
Δ: It became tack-free within 2 hours or 12 hours.
X: It did not become tack-free even after 12 hours.

(Evaluation of hardness)
The surface hardness of the cured product having a thickness of about 2 mm was evaluated at 23 ° C. by the method described in "JIS K5600-5-4, scratch hardness (pencil method)".

[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 as a dispersion stabilizer (ketenization degree: 80%, polymerization degree: 1). , 700) 0.5 part was added and stirred. After the polyvinyl alcohol was completely dissolved, stirring was stopped, and 60 parts of methyl methacrylate, 40 parts of n-butyl methacrylate, 0.1 part of 2,2'-azobisisobutyronitrile, and 0.5 part of n-octyl mercaptan. Was added and the mixture was stirred again. The atmosphere in the polymerization apparatus was replaced with nitrogen under stirring, and the temperature was raised to 70 ° C. for polymerization. After detecting the peak of the heat of polymerization, the temperature was raised to 98 ° C., the reaction was further carried out for 0.5 hour, 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 mass average molecular weight (Mw) of the polymer 1 was 42,000.

[Example 1]
In a reaction vessel equipped with a cooler, 58 parts of methyl methacrylate (MMA), 10 parts of 2-ethylhexyl acrylate (2-EHA), and 2 parts of triethylene glycol dimethacrylate (acryester 3ED) as component (A). , 1 part of N, N'-di-n-butylthiourea (dibutylthiourea) as a component (B), 3 parts of tridecylphosphite (Adecastab 3010) as a component (D), and 0. BHT as a polymerization inhibitor. 03 parts, as paraffin wax, 0.4 parts of paraffin 115, 0.3 parts of paraffin 130, 0.2 parts of paraffin 150 were added, and these components in the reaction vessel were stirred and produced as the component (E). 30 parts of the polymer 1 produced in Example 1 was added. Next, the temperature of the solution in the reaction vessel was raised to 60 ° C., and the mixture was stirred for 2 hours while maintaining the temperature. After confirming that the polymer 1 was completely dissolved, the mixture was cooled to 23 ° C. Further, 3 parts of t-hexyl peroxyisopropyl carbonate (perhexyl I) was added as a component (C) to obtain a curable resin composition.

A frame of 10 cm × 15 cm is provided on the PET film with a urethane sponge having a thickness of 2 mm and a adhesive, and the curable resin composition is poured into the frame so as to have a thickness of about 2 mm and allowed to stand in an atmosphere of 23 ° C. for 12 hours. Then, a cured product having a thickness of about 2 mm was obtained.

The curability of the curable resin composition and the hardness of the cured product having a thickness of about 2 mm were evaluated. The results are shown in Table 1.

[Examples 2 to 16]
A curable resin composition and a cured product having a thickness of 2 mm were prepared in the same manner as in Example 1 except that the composition was changed as shown in Table 1, and each evaluation was performed.

[Comparative Example 1]
In Comparative Example 1, as shown in Table 1, a curable resin composition and a cured product having a thickness of 2 mm were prepared and evaluated in the same manner as in Example 1 except that the component (D) was not blended. It was. In the evaluation of curability, the hardness was not evaluated because it did not become tack-free even after 12 hours.

[Comparative Example 2]
In Comparative Example 2, as shown in Table 1, the curable resin composition and the curable resin composition were the same as in Example 1 except that the component (C) was not blended and the hydroperoxide Kayakmen H was used as the curing agent. A cured product having a thickness of 2 mm was prepared, and each evaluation was performed. In the evaluation of hardness, even 6B was scratched, so the evaluation result was set to "6B>".

As shown in Table 1, in each of Examples 1 to 16, the curability of the curable resin composition and the hardness of the cured product were good. On the other hand, Comparative Example 1 had poor curability and was not tack-free. Further, in Comparative Example 2, the hardness of the cured product was remarkably low.

The abbreviations in the table are as follows.
MMA: Methyl Methacrylate, manufactured by Mitsubishi Rayon, Acriester M (trade name).
2-EHA: 2-ethylhexyl acrylate, manufactured by Mitsubishi Chemical Corporation, also known as -2-ethylhexyl acrylate.
Acriester 3ED (trade name): Triethylene glycol dimethacrylate, manufactured by Mitsubishi Rayon.
Dibutylthiourea: N, N'-dibutylthiourea, manufactured by Wako Pure Chemical Industries, Ltd.
Diethylthiourea: N, N'-diethylthiourea, manufactured by Wako Pure Chemical Industries, Ltd.
Perhexyl I (trade name): t-hexyl peroxyisopropyl carbonate, manufactured by NOF CORPORATION.
Trigonox 117 (trade name): t-butylperoxy2-ethylhexyl carbonate, manufactured by Kayaku Akzo.
Kayalen 6-70 (trade name): 1,6-bis (t-butylperoxycarbonyloxy) hexane, manufactured by Kayaku Akzo.
Luperox TAIC M75 (trade name): t-amylperoxyisopropyl carbonate, manufactured by Arkema Yoshitomi.
Luperox TAEC (trade name): t-amylperoxy2-ethylhexyl carbonate, manufactured by Arkema Yoshitomi.
ADEKA STAB 3010 (trade name): Tridecylphosfite, manufactured by ADEKA.
JP-308E (trade name): Tris (2-ethylhexyl) phosphite, manufactured by Johoku Chemical Industry Co., Ltd.
JP-318-O (trade name): Trioleyl phosphite, manufactured by Johoku Chemical Industry Co., Ltd.
JPS-321 (trade name): Trilauryl trithiophosphite, manufactured by Johoku Chemical Industry Co., Ltd.
Hokuko TPP (trade name): Triphenylphosphine, manufactured by Hokuko Chemical Industry Co., Ltd.
Polymer 1: The polymer produced in Production Example 1, a copolymer of methyl methacrylate / n-butyl methacrylate = 60/40 (monomer mass ratio), Mw = 42,000.
BHT: 2-6-di-t-butyl-4-methylphenol, manufactured by Honshu Chemical Industry Co., Ltd., trade name: "H-BHT".
Paraffin 115: Paraffin wax (melting point described in the catalog: 47 ° C.), manufactured by Nippon Seiro Co., Ltd.
Paraffin 130: Paraffin wax (melting point described in the catalog: 55 ° C.), manufactured by Nippon Seiro Co., Ltd.
Paraffin 150: Paraffin wax (melting point described in the catalog: 66 ° C.), manufactured by Nippon Seiro Co., Ltd.
Kayakumen H (trade name): Cumene hydroperoxide, manufactured by Kayaku Akzo.

According to the embodiment of the present invention, a curable resin composition having good curability at room temperature even in the presence of oxygen and a cured product having excellent hardness can be obtained, a cured product thereof, and a coating material composed of the cured product. It is extremely useful industrially because it can provide.

Claims (6)

(A) Radical-polymerizable vinyl-based monomer component,
(B) Thiourea compound component,
(C) peroxide component having the structure of formula (1), and viewed including the (D) (A) organophosphorus compound component other than the component, the component (D) of the phosphite compound and phosphine compound A curable resin composition containing at least one .

(In formula (1), R is a hydrocarbon group having 1 to 15 carbon atoms.) Further, the (E) (meth) acrylic polymer component may be contained as an optional component.
The content of the component (A) is 5 to 100% by mass with respect to the total amount of the component (A) and the component (E).
The content of the component (E) is 0 to 95% by mass with respect to the total amount of the component (A) and the component (E).
The content of the component (B) is 0.05 to 5 parts by mass with respect to 100 parts by mass of the total amount of the component (A) and the component (E).
The content of the component (C) is 0.1 to 10 parts by mass with respect to 100 parts by mass of the total amount of the component (A) and the component (E).
The curable resin composition according to claim 1, wherein the content of the component (D) is 0.1 to 10 parts by mass with respect to 100 parts by mass of the total amount of the component (A) and the component (E). object. The curable resin composition according to claim 2, wherein the content of the component (E) is 1 to 50% by mass with respect to the total amount of the component (A) and the component (E). The curable resin composition according to any one of claims 1 to 3 , which contains a (meth) acrylic monomer as a component (A). A cured product of the curable resin composition according to any one of claims 1 to 4 . A coating material comprising the curable resin composition according to any one of claims 1 to 4 .